CN101537372A - Modification method for titanium-silicon molecular sieve - Google Patents
Modification method for titanium-silicon molecular sieve Download PDFInfo
- Publication number
- CN101537372A CN101537372A CN200810102305A CN200810102305A CN101537372A CN 101537372 A CN101537372 A CN 101537372A CN 200810102305 A CN200810102305 A CN 200810102305A CN 200810102305 A CN200810102305 A CN 200810102305A CN 101537372 A CN101537372 A CN 101537372A
- Authority
- CN
- China
- Prior art keywords
- accordance
- source
- hts
- titanium
- molecular sieve
- 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.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
A modification method for a titanium-silicon molecular sieve comprises the following steps of mixing the titanium-silicon molecular sieve, a titanium source, a protective agent, an alkali source, a noble metal source, a reducing agent and water according to the proportion of 100:(0.001-1):(0.0001-5):(0.005-5):(0.005-10):(0.005-20):(500-10,000), and carrying out hydro-thermal treatment, wherein the protective agent is selected from one or more of polybenzimidazole, polypropylene, polyethyleneglycol, polystyrene, polyvinyl chloride, polyethylene and derivatives thereof, an anionic surfactant, a cationic surfactant, a non-ionic surfactant, glucose and cyclodextrin; and the reducing agent is selected from one or more of hydrazine, borohydride and sodium citrate. The titanium-silicon molecular sieve prepared by the method has high content of framework titanium and has high oxidation activity and selectivity as well as good stability.
Description
Technical field
The present invention relates to a kind of method of modifying of HTS.
Background technology
HTS is the novel hetero-atom molecular-sieve of early eighties exploitation in last century.The MCM-22 of the at present synthetic TS-1 that MFI type structure is arranged, the TS-2 of MEL type structure, MWW type structure and have than the TS-48 of macroporous structure etc.HTS can be used for the multiple organic oxidizing reaction of catalysis, for example alkene epoxidation, partial oxidation of alkanes, oxidation of alcohols, phenols hydroxylating, cyclic ketones ammoxidation, and in the reaction, can adopt free of contamination low concentration hydrogen peroxide as oxidant, the selectivity height of reaction has unrivaled energy-conservation, economy of conventional oxidation system and environmental friendliness advantage.HTS is considered to a milestone in molecular sieve catalytic field as the organic matter catalyst for selective oxidation.
H
2O
2Be the green oxidation agent of generally acknowledging, its oxidized byproduct has only water, but H
2O
2Extremely unstable, meet heat, light, rough surface, heavy metal and other impurity and can decompose, and have corrosivity so H
2O
2In packing, storage, transportation, to take special safety measure.People consider H for this reason
2O
2Use on the spot, or with H
2O
2Production technology with use H
2O
2Downstream process combine.
Utilize H
2And O
2Can directly synthesize H
2O
2, and atom utilization reaches 100%, and then people expect utilizing H
2And O
2Come original position to synthesize H
2O
2Reoxidize Organic Ingredients to solve indirect utilization H
2O
2Cost and safety problem.This technological reaction mild condition, selectivity good (can reach more than 95%), present subject matter are that catalyst activity is low, poor stability, H
2Effective rate of utilization is low.
Pt, Pd, Au etc. are catalysis H
2And O
2Synthetic H
2O
2Active principle, many bibliographical informations utilize it that titanium silicalite material is carried out modification to come original position to generate H
2O
2Be used for the organic matter selective oxidation reaction.For example, and Meiers R. etc. (J._Catal., 1998, be that catalyst is studied propylene gas-phase epoxidation with Pt-Pd/TS-1 176:376-386); US 6867312B1 and US 6884898B1 etc. have also carried out the research of this respect.
CN1260241A discloses the method for modifying of a kind of HTS (TS-1), this method comprises the hydrating solution of titanium and the TS-1 molecular sieve that has synthesized according to molecular sieve (gram): Ti (mole)=(200～1500): 1 ratio mixes, the gained mixture was reacted under 120～200 ℃ temperature 1～8 day in reactor, filter, wash and drying, obtain adding the synthetic TS-1 molecular sieve of titanium; This method gained TS-1 framework of molecular sieve titaniferous amount is improved.
CN1245090A discloses the method for modifying of a kind of HTS (TS-1), and this method comprises that TS-1 molecular sieve, acid compound and the water that will synthesize mix, and reacts 5 minutes down to 6h at 5～95 ℃, obtains acid-treated TS-1 molecular sieve; Gained is mixed through acid-treated TS-1 molecular sieve, organic base and water, and in sealed reactor under 120～200 ℃ temperature and self-generated pressure 2h to the 8 day time of reaction, then products therefrom is filtered, washing and dry; This method gained TS-1 molecular sieve has reduced the invalid decomposition of oxidant, thereby its catalytic oxidation activity is compared with prior art obviously improved owing to removed the outer titanium of skeleton in the part molecular sieve pore passage, has stability of catalytic activity preferably simultaneously.
Summary of the invention
The method of modifying that the purpose of this invention is to provide a kind of new micropore titanium silicon molecular sieve material.
The invention provides a kind of HTS method of modifying, may further comprise the steps:
(1) with HTS, titanium source, protective agent, alkali source, noble metal source, reducing agent, water according to 100: (0.001～1): (0.0001～5): (0.005～5): (0.005～10): (0.005～20): the ratio of (500～10000) is mixed; Wherein HTS is in the gram number, and noble metal source is in the gram number of precious metal simple substance, and titanium source, protective agent, alkali source, reducing agent, water are in molal quantity; Described protective agent is selected from one or more in polybenzimidazoles, polypropylene, polyethylene glycol, polystyrene, polyvinyl chloride, polyethylene and their derivative, anion surfactant, cationic surfactant, non-ionic surface active agent, glucose and the cyclodextrin, and described reducing agent is selected from one or more in hydrazine, boron hydride, the natrium citricum;
(2) with the mixture hydrothermal treatment consists of step (1) gained, reclaim molecular sieve.
HTS method of modifying provided by the invention can make total titanium amount of molecular sieve improve, and makes the outer titanium of skeleton enter skeleton, reduces the extra-framework titanium amount, (adopts 960cm in the infrared spectrum usually thereby increase effective skeleton titanium amount
-1Place's absworption peak and 550cm
-1The absorption intensity ratio I of place's absworption peak
960/ I
550Characterize the relative Ti content in the HTS skeleton, I
960/ I
550Ti content is high more relatively in the big more expression skeleton), the synergy of noble metal and titanium-silicon molecular screen material is improved; The inventive method is introduced reducing agent in preparation process, noble metal is activated at low-temperature reduction, has overcome the drawback that the reduction activation noble metal is assembled under the high temperature; Operation is simple for the inventive method, and modifying process is controlled easily.The modified micropore titanium silicalite material of the inventive method preparation, its catalytic oxidation activity, selectivity height, good stability.
The specific embodiment
In the HTS method of modifying provided by the invention; HTS in the step (1): titanium source: protective agent: alkali: noble metal source: reducing agent: water is preferably 100: (0.005～1): (0.005～1): (0.01～2): (0.01～5): (0.01～10): (500～5000); wherein HTS is in the gram number; noble metal source is in the gram number of precious metal simple substance, and titanium source, protective agent, alkali source, reducing agent, water are in molal quantity.
In the HTS method of modifying provided by the invention, described polybenzimidazoles, polypropylene, polyethylene glycol, polystyrene, polyvinyl chloride, poly derivative is the polybenzimidazoles pyrrolidones, polybenzimidazoles alcohol, the polybenzimidazoles ether, the polybenzimidazoles pyrimidine, the polypropylene pyrrolidones, POLYPROPYLENE GLYCOL, the polypropylene ether, the polypropylene pyrimidine, the polyethylene glycol pyrrolidones, the polyethylene glycol ether, the polyethylene glycol pyrimidine, the polystyrene pyrrolidones, polystyrene alcohol, the polystyrene ether, the polystyrene pyrimidine, the polyvinyl chloride pyrrolidones, polyvinyl chloride alcohol, the polyvinyl chloride ether, the polyvinyl chloride pyrimidine, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl ethyl ether and polyethylene pyrimidine.
In the HTS method of modifying provided by the invention, described anion surfactant is soap for example, sulfuric acid, phosphate ester salt, alkylbenzenesulfonate, alpha-alkene sulfonate, alkylsulfonate, the alpha-sulfo monocarboxylate, aliphatic acid sulfoalkyl ester, sulphosuccinates, alkylnaphthalene sulfonate, petroleum sulfonate, lignosulfonates, alkyl glyceryl ether sulfonate etc., cationic surfactant is for example: fatty amine quaternary cationics, the ring-type cationic surfactant, softex kw, DDAO, three sufferings (ninth of the ten Heavenly Stems) ylmethyl chlorine (bromine) are changed ammonium, and non-ionic surface active agent is AEO for example, the block polyoxyethylene polyoxypropylene ether, alkylolamides, the polyol ester class, tween series, sapn series, fluorocarbon surfactant series.
In the method for modifying provided by the present invention, the described noble metal source of step (1) is selected from other complex compound of oxide, halide, carbonate, nitrate, acetate, ammonium salt, sal-ammoniac salt, hydroxide and the noble metal of noble metal, and described other complex compound is noble metal and complex compound, noble metal and the cyclo-octadiene of acetylacetone,2,4-pentanedione and the complex compound that cyclo-octatriene forms for example.For example when described noble metal was palladium, noble metal source can be one or more in palladium oxide, carbonate palladium, palladium bichloride, palladium nitrate, nitric acid ammonia palladium, sal-ammoniac palladium, palladium dydroxide, palladium, the palladium acetylacetonate.Preferred palladium of described noble metal and/or platinum.
In the method for modifying provided by the invention, the described alkali source of step (1) is inorganic base or organic base.Wherein inorganic base is one or more in ammoniacal liquor, NaOH, potassium hydroxide, the barium hydroxide; Organic base is one or more in urea, quaternary amine alkali compounds, fat amine compound, the alcamine compound, is preferably the quaternary amine alkali compounds.
Described its general formula of quaternary ammonium base compounds is (R
1)
4NOH, wherein R
1For having the alkyl of 1～4 carbon atom, be preferably propyl group.
Its general formula of described fat amine compound is R
2(NH
2)
n, R wherein
2Be selected from alkyl or alkylidene with 1～6 carbon atom, n=1 or 2 is preferably ethamine, n-butylamine, butanediamine or hexamethylene diamine.
Its general formula of described alcamine compound is (HOR
3)
mNH
(3-m)R wherein
3Be selected from alkyl with 1～4 carbon atom; M=1,2 or 3.Described alcamine compound is MEA, diethanol amine or triethanolamine for example.
In the method provided by the present invention, the described titanium of step (1) source can be inorganic titanium-containing compound such as TiCl
4, TiOCl
2, Ti (SO
4)
2Deng, also can be for example titanate esters Ti (OR of organic titanium-containing compound
4)
4, R wherein
4For having the alkyl of 2～5 carbon atoms, be preferably butyl.
Among the preparation method provided by the invention, the reducing agent described in the step (1) is selected from one or more in hydrazine, boron hydride, the natrium citricum, and wherein hydrazine can be hydrazine hydrate, hydrazine hydrochloride, hydrazine sulfate, and boron hydride can be sodium borohydride, potassium borohydride.
In the method for modifying provided by the invention, the described charging sequence that HTS, titanium source, protective agent, palladium source, reducing agent and alkali source are mixed is preferably HTS, titanium source, protective agent, palladium source, reducing agent is joined in the solution of alkali source.
In the method for modifying provided by the invention, the hydro-thermal treatment method in the synthetic or HTS modification carries out the described hydrothermal treatment consists of step (2) according to existing HTS, is included in hydrothermal treatment consists 2～360h under 80～200 ℃ of temperature and the self-generated pressure.
In the method for modifying that provides of invention, described recovery comprises filtrations, washing, drying, calcination steps, can according to HTS in the prior art synthesize or modification in recovery method carry out, the present invention does not have specific (special) requirements.Described washing can be adopted distilled water or deionized water washing; The condition of described drying is room temperature～200 ℃, air atmosphere, drying time 3～24h; Described roasting condition is 300～600 ℃, nitrogen or air atmosphere, roasting time 3～24h.
Method of modifying provided by the invention can be used for the HTS modification, described HTS is TS-1 for example, TS-2, Ti-BETA, Ti-MCM-22, Ti-MCM-41 or Ti-MCM-48, also can be that these molecular sieves are through having method modification (for example introducing noble metal by the method for dipping) now or according to the modifying titanium-silicon molecular sieve that the inventive method modification obtains, being preferably the TS-1 molecular sieve.Described TS-1 molecular sieve can be according to the synthetic TS-1 molecular sieve of any method of the prior art, can through or without calcination process, contain or do not contain organic formwork agent.
Following embodiment will the present invention is further illustrated, but therefore do not limit the present invention.Used reagent is commercially available chemically pure reagent among the embodiment.Used HTS is by Zeolites among Comparative Examples and the embodiment, 1992, and the TS-1 molecular sieve of the method preparation described in the 943rd～950 page of the Vol.12.The sieve sample infrared spectrum is measured on Nicolet 8210 type Fourier infrared spectrographs, KBr compressing tablet, test specification 400～4000cm
-1The I of TS-1 molecular sieve, Comparative Examples and the resulting sample of embodiment
960/ I
550Data are listed in table 1.
Comparative Examples 1
This Comparative Examples explanation conventional method prepares the process of load type palladium/titanium-silicon molecular sieve catalyst (0.5%Pd/TS-1).
Get 20 gram titanium-silicon molecular sieve TS-1s and concentration and be 20mL deionized water for stirring that the nitric acid ammonia palladium complex solution 2.0mL of 0.05g/mL (in the palladium atom) joins evenly after, sealing, under 40 ℃ of temperature, flood 24h, drying at room temperature is 12 hours then, reduction activation 5h under 300 ℃, in the hydrogen atmosphere promptly gets conventional load type palladium/titanium-silicon molecular sieve catalyst (0.5%Pd/TS-1) DB-1.
Embodiment 1
Getting 20 gram titanium-silicon molecular sieve TS-1s, concentration is nitric acid ammonia palladium complex solution, the TiCl of 0.01g/mL (in the palladium atom)
4, hydrazine hydrate and softex kw join in the aqueous solution (mass percent concentration 10%) of TPAOH and stir, HTS (gram): TiCl wherein
4(mole): softex kw (mole): TPAOH (mole): nitric acid ammonia palladium complex (gram is in palladium): hydrazine hydrate (mole): water (mole)=100: 0.1: 0.005: 0.5: 2.0: 3.0: 1000.Put into the stainless steel sealed reactor then, hydrothermal treatment consists 48h under 150 ℃ temperature and self-generated pressure filters, washing, and drying at room temperature, roasting 5h in 550 ℃ nitrogen atmosphere promptly gets the modified micropore HTS again, is designated as A.
Embodiment 2
Getting 20 gram titanium-silicon molecular sieve TS-1s, concentration is palladium chloride solution, the Ti (SO of 0.01g/mL (in the palladium atom)
4)
2, hydrazine hydrochloride and polyacrylate join in the aqueous solution (mass percent concentration 15%) of NaOH and stir, HTS (gram) wherein: Ti (SO
4)
2(mole): polyacrylate (mole): NaOH (mole): palladium bichloride (gram is in palladium): hydrazine hydrochloride (mole): water (mole)=100: 0.5: 0.9: 1.0: 0.15: 0.1: 1600.Put into the stainless steel sealed reactor then, hydrothermal treatment consists 24h under 180 ℃ temperature and self-generated pressure filters, washs, dry 3h under 110 ℃, and roasting 5h in 450 ℃ of following nitrogen atmospheres promptly gets modified micropore HTS B.
Embodiment 3
Getting 20 gram titanium-silicon molecular sieve TS-1s, concentration is palladium nitrate solution, the TiOCl of 0.01g/mL (in the palladium atom)
2And right amount of boron sodium hydride and Tween 80 join in the aqueous solution (mass percent concentration 10%) of TPAOH and butanediamine and stir, wherein HTS (gram): (mole is with TiO in the titanium source
2Meter): protective agent (mole): alkali source (mole): palladium source (gram; in palladium): reducing agent (mole): water (mole)=100: 0.01: 0.03: 0.1: 0.05: 0.02: 550; put into sealed reactor then; hydrothermal treatment consists 120h under 120 ℃ temperature and self-generated pressure; filter, wash; at 150 ℃ of following dry 3h, roasting 5h in 350 ℃ of following nitrogen atmospheres gets modified micropore HTS C then.
Embodiment 4
Get 20 gram titanium-silicon molecular sieve TS-1s, butyl titanates, concentration and be in the aqueous solution (mass percent concentration 15%) that the sal-ammoniac palladium solution of 0.02g/mL (in the palladium atom) and an amount of hydrazine sulfate and neopelex join TPAOH and stir, HTS (gram) wherein: (mole is with TiO in the titanium source
2Meter): protective agent (mole): alkali source (mole): palladium source (gram; in palladium): reducing agent (mole): water (mole)=100: 0.005: 2.0: 0.8: 1.0: 2.0: 2500; put into the stainless steel sealed reactor then; hydrothermal treatment consists 96h under 150 ℃ temperature and self-generated pressure; filter, wash; dry 3h under 120 ℃, roasting 5h in 550 ℃ of following nitrogen atmospheres gets modified micropore HTS D.
Embodiment 5
Get 20 gram titanium-silicon molecular sieve TS-1s, tetraethyl titanates, concentration and be in the aqueous solution (mass percent concentration 10%) that the ammonium nitrate palladium solution of 0.01g/mL (in the palladium atom) and right amount of boron sodium hydride and polyvinylpyrrolidone (relative molecular mass is 15000) join butanediamine and stir, HTS (gram) wherein: tetraethyl titanate (mole): polyvinylpyrrolidone (mole): butanediamine (mole): acid chloride (gram is in palladium): sodium borohydride (mole): water (mole)=100: 0.05: 0.001: 0.05: 0.02: 0.05: 800.Put into the stainless steel sealed reactor then, hydrothermal treatment consists 120h under 120 ℃ temperature and self-generated pressure filters, washing, and dry 3h under 150 ℃, roasting 5h in 550 ℃ of following nitrogen atmospheres gets modified micropore HTS E.
Embodiment 6
Get 20 gram titanium-silicon molecular sieve TS-1s, the metatitanic acid orthocarbonate, concentration is that the sal-ammoniac palladium solution of 0.05g/mL (in the palladium atom) and an amount of hydrazine sulfate and neopelex join in the aqueous solution (mass percent concentration 10%) of TPAOH, stir, HTS (gram) wherein: metatitanic acid orthocarbonate (mole): neopelex (mole): TPAOH (mole): hydrazine sulfate (mole): sal-ammoniac palladium (gram, in palladium): reducing agent (mole): water (mole)=100: 0.8: 0.1: 2.0: 5.0: 10.0: 4800, put into the stainless steel sealed reactor then, hydrothermal treatment consists 240h under 90 ℃ temperature and self-generated pressure, filter, washing, dry 3h under 120 ℃, roasting 5h in 550 ℃ of following nitrogen atmospheres gets modified micropore HTS F.
Embodiment 7
Get 20 gram titanium-silicon molecular sieve TS-1s, tetraethyl titanate, palladium dydroxide, polybenzimidazoles (density 1.2g/cm
3) and natrium citricum join in the TPAOH (mass percent concentration 13%) and stir, HTS (gram) wherein: (mole is with TiO in the titanium source
2Meter): protective agent (mole): alkali source (mole): palladium source (gram; in palladium): reducing agent (mole): water (mole)=100: 0.3: 5.0: 0.01: 0.5: 1.0: 2000; put into the stainless steel sealed reactor then; hydrothermal treatment consists 120h under 160 ℃ temperature and self-generated pressure; filter, washing is at 150 ℃ of dry 3h; roasting 5h in 550 ℃ of following nitrogen atmospheres gets modified micropore HTS G.
Embodiment 8
Get 20 gram titanium-silicon molecular sieve TS-1s, butyl titanates, concentration and be in the aqueous solution (mass percent concentration 15%) that the nitric acid ammonia palladium solution of 0.05g/mL (in the palladium atom) and an amount of hydrazine hydrate and cyclodextrin join TPAOH and stir, HTS (gram) wherein: (mole is with TiO in the titanium source
2Meter): protective agent (mole): alkali source (mole): palladium source (gram; in palladium): reducing agent (mole): water (mole)=100: 1.0: 3.2: 1.5: 3.0: 8.2: 3500; put into the stainless steel sealed reactor then; hydrothermal treatment consists 48h under 120 ℃ temperature and self-generated pressure; filter, wash; dry 3h under 120 ℃, roasting 5h in 550 ℃ of following nitrogen atmospheres gets modified micropore HTS H.
Embodiment 9
Get 20 gram titanium-silicon molecular sieve TS-1s, butyl titanate, palladium oxide and an amount of natrium citricum and glucose join in the aqueous solution (mass percent concentration 18%) of triethanolamine, stir, HTS (gram) wherein: butyl titanate (mole): glucose (mole): triethanolamine (mole): natrium citricum (mole): palladium oxide (gram, in palladium): reducing agent (mole): water (mole)=100: 0.02: 0.02: 1.2: 4.0: 6.0: 1200, put into reactor then, hydrothermal treatment consists 320h under 130 ℃ temperature and self-generated pressure, filter, washing, dry 3h under 120 ℃, roasting 5h in 550 ℃ of following nitrogen atmospheres gets modified micropore HTS I.
Embodiment 10
20 gram titanium-silicon molecular sieve TS-1s, tetraethyl titanates, palladium acetylacetonate, potassium borohydride and softex kw joined in the TPAOH (mass percent concentration 13%) mix, HTS (gram) wherein: (mole is with TiO in the titanium source
2Meter): protective agent (mole): alkali source (mole): palladium source (gram; in palladium): reducing agent (mole): water (mole)=100: 0.2: 0.5: 1.8: 0.8: 0.5: 4000; put into the stainless steel sealed reactor then; hydrothermal treatment consists 120h under 160 ℃ temperature and self-generated pressure; filter, wash; and under 150 ℃, continuing dry 3h, roasting 5h in 550 ℃ of following nitrogen atmospheres promptly gets the micropore titanium silicon molecular sieve J of the present invention through modification again.
Comparative Examples 2
The conventional dipping of this Comparative Examples explanation method of modifying prepares load type palladium-platinum/HTS (0.5%Pd, process 0.5%Pt/TS-1).
Get 20 gram titanium-silicon molecular sieve TS-1s and concentration and be the nitric acid ammonia palladium of 0.05g/mL (in the palladium atom) and 20mL deionized water for stirring that each 2.0mL of nitric acid ammonia platinum complex solution joins evenly after, suitably sealing, temperature is at 40 ℃ of dipping 24h down.Air dry then, and in 300 ℃ of following hydrogen atmospheres, carry out reduction activation 5h, promptly get conventional load type palladium-platinum/titanium-silicon molecular sieve catalyst (0.5%Pd, 0.5%Pt/TS-1) DB-2.
Embodiment 11
Get 20 gram titanium-silicon molecular sieve TS-1s, butyl titanate, concentration is that the nitric acid ammonia palladium of 0.01g/mL (in the palladium atom) and nitric acid ammonia platinum complex solution and hydrazine hydrate and softex kw join in the aqueous solution (mass percent concentration 16%) of TPAOH and stir, HTS (gram) wherein: butyl titanate (mole): softex kw (mole): TPAOH (mole): nitric acid ammonia platinum (gram, in platinum): nitric acid ammonia palladium (gram is in palladium): hydrazine hydrate (mole): water (mole)=100: 0.02: 0.02: 1.6: 0.1: 0.05: 5.5: 1800.Put into the stainless steel sealed reactor then, hydrothermal treatment consists 72h under 160 ℃ temperature and self-generated pressure filters, washs, air dry under the room temperature, and roasting 5h in 550 ℃ of following nitrogen atmospheres gets modified micropore HTS K.
Table 1
| Sample source | Sample number into spectrum | I 960/I 550 |
| Press the synthetic TS-1 of document | 0.685 | |
| Embodiment 1 | A | 0.713 |
| Embodiment 2 | B | 0.718 |
| Embodiment 3 | C | 0.714 |
| Embodiment 4 | D | 0.707 |
| Embodiment 5 | E | 0.710 |
| Embodiment 6 | F | 0.696 |
| Embodiment 7 | G | 0.708 |
| Embodiment 8 | H | 0.705 |
| Embodiment 9 | I | 0.712 |
| Embodiment 10 | J | 0.704 |
| Embodiment 11 | K | 0.701 |
| Comparative Examples 1 | DB-1 | 0.678 |
| Comparative Examples 2 | DB-2 | 0.672 |
By table 1 as seen, the sample I of the inventive method preparation
960/ I
550Value is than the I of TS-1 molecular sieve and comparative example
960/ I
550Value is high, and the relative Ti content height of sample skeleton of the inventive method preparation is described.
Embodiment 12
Present embodiment illustrates that the sample of embodiment sample provided by the invention and Comparative Examples preparation is used for hydrogen, there is the effect of preparing epoxypropane by epoxidation of propene reaction down in oxygen.
Getting each 0.5g of the prepared sample of the foregoing description and Comparative Examples respectively joins in the epoxidation reaction container that contains methyl alcohol 60mL, feed propylene, oxygen, hydrogen and nitrogen, (mol ratio is 1: 1: 1: 7) to form propylene-oxygen-hydrogen-nitrogen mixture atmosphere, 40 ℃ of temperature, pressure 2.0MPa, the propylene air speed is 10h
-1Condition under, carry out epoxidation reaction and generate expoxy propane (PO).
Propylene conversion and the PO selectivity of reaction 2h and 12h the results are shown in Table 2.
Table 2
By table 1 as seen, the sample of the inventive method preparation is used for propylene ring oxidation reaction, active, PO selectivity height, good stability.
Claims (18)
1. a HTS method of modifying comprises the following steps:
(1) with HTS, titanium source, protective agent, alkali source, noble metal source, reducing agent, water according to 100: (0.001～1): (0.0001～5): (0.005～5): (0.005～10): (0.005～20): the ratio of (500～10000) is mixed; Wherein HTS is in the gram number, and noble metal source is in the gram number of precious metal simple substance, and titanium source, protective agent, alkali source, reducing agent, water are in molal quantity; Described protective agent is selected from one or more in polybenzimidazoles, polypropylene, polyethylene glycol, polystyrene, polyvinyl chloride, polyethylene and their derivative, anion surfactant, cationic surfactant, non-ionic surface active agent, glucose and the cyclodextrin, and described reducing agent is selected from one or more in hydrazine, boron hydride, the natrium citricum;
(2) with the mixture hydrothermal treatment consists of step (1) gained, reclaim molecular sieve.
2. in accordance with the method for claim 1; it is characterized in that HTS in the step (1): titanium source: protective agent: alkali: noble metal source: reducing agent: water=100: (0.005～1): (0.005～1): (0.01～2): (0.01～5): (0.01～10): (500～5000).
3. in accordance with the method for claim 1, it is characterized in that described polybenzimidazoles, polypropylene, polyethylene glycol, polystyrene, polyvinyl chloride, poly derivative is the polybenzimidazoles pyrrolidones, polybenzimidazoles alcohol, the polybenzimidazoles ether, the polybenzimidazoles pyrimidine, the polypropylene pyrrolidones, POLYPROPYLENE GLYCOL, the polypropylene ether, the polypropylene pyrimidine, the polyethylene glycol pyrrolidones, the polyethylene glycol ether, the polyethylene glycol pyrimidine, the polystyrene pyrrolidones, polystyrene alcohol, the polystyrene ether, the polystyrene pyrimidine, the polyvinyl chloride pyrrolidones, polyvinyl chloride alcohol, the polyvinyl chloride ether, the polyvinyl chloride pyrimidine, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl ethyl ether, the polyethylene pyrimidine.
4. in accordance with the method for claim 1, wherein the described noble metal source of step (1) is selected from oxide, halide, carbonate, nitrate, ammonium salt, chlorination ammonium salt, the hydroxide of noble metal.
5. according to claim 1 or 4 described methods, it is characterized in that wherein said noble metal is palladium and/or platinum.
6. in accordance with the method for claim 1, it is characterized in that the alkali source described in the step (1) is one or more in ammoniacal liquor, NaOH, potassium hydroxide, barium hydroxide, urea, quaternary amine alkali compounds, fat amine compound, the alcamine compound.
7. in accordance with the method for claim 6, it is characterized in that described its general formula of quaternary ammonium base compounds is (R
1)
4NOH, wherein R
1For having the alkyl of 1～4 carbon atom.
8. in accordance with the method for claim 7, it is characterized in that described R
1Be propyl group.
9. in accordance with the method for claim 6, it is characterized in that its general formula of described fat amine compound is R
2(NH
2)
n, R wherein
2Be selected from alkyl or alkylidene, n=1 or 2 with 1～6 carbon atom.
10. in accordance with the method for claim 9, it is characterized in that described fat amine compound is ethamine, n-butylamine, butanediamine or hexamethylene diamine.
11. in accordance with the method for claim 6, its general formula of wherein said alcamine compound is (HOR
3)
mNH
(3-m)R wherein
3Be selected from alkyl, m=1,2 or 3 with 1～4 carbon atom.
12. in accordance with the method for claim 11, it is characterized in that described alcamine compound is MEA, diethanol amine or triethanolamine.
13. in accordance with the method for claim 1, it is characterized in that described titanium source is TiCl
4, TiOCl
2, Ti (SO
4)
2With organic titanate Ti (OR
4)
4In one or more, R wherein
4For having the alkyl of 2～5 carbon atoms.
14. in accordance with the method for claim 1, it is characterized in that described hydrazine is one or more in hydrazine hydrate, hydrazine hydrochloride and the hydrazine sulfate, described boron hydride is sodium borohydride and/or potassium borohydride.
15. in accordance with the method for claim 1; it is characterized in that the described charging sequence that HTS, titanium source, protective agent, noble metal source, reducing agent and alkali source are mixed is for to join HTS, titanium source, protective agent, noble metal source, reducing agent in the solution that contains alkali source.
16. in accordance with the method for claim 1, it is characterized in that the temperature of the described hydrothermal treatment consists of step (2) is 80～200 ℃, pressure is self-generated pressure, and the time is 2～360h.
17. in accordance with the method for claim 1, it is characterized in that the described HTS of step (1) is TS-1, TS-2, Ti-MCM-41, Ti-MCM-48, Ti-BETA or Ti-MCM-22.
18. a metal-modified HTS is characterized in that, described molecular sieve is according to each described method preparation of claim 1～17.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101023058A CN101537372B (en) | 2008-03-20 | 2008-03-20 | Modification method for titanium-silicon molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101023058A CN101537372B (en) | 2008-03-20 | 2008-03-20 | Modification method for titanium-silicon molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101537372A true CN101537372A (en) | 2009-09-23 |
| CN101537372B CN101537372B (en) | 2011-12-21 |
Family
ID=41120892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101023058A Active CN101537372B (en) | 2008-03-20 | 2008-03-20 | Modification method for titanium-silicon molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101537372B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183356A (en) * | 2011-12-30 | 2013-07-03 | 中国石油化工股份有限公司 | Method for modifying titanium silicalite molecular sieve by precious metal source |
| US9486790B2 (en) | 2011-10-31 | 2016-11-08 | Dalian University Of Technology | Modification method of titanium-silicalite zeolite based on the mixture of quaternary ammonium salt and inorganic alkali |
| CN107879355A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Modified with noble metals HTS and its preparation method and application and a kind of method of alkene direct oxidation |
| CN107965661A (en) * | 2017-12-08 | 2018-04-27 | 芜湖市海格瑞德科技有限责任公司 | A kind of high stability liquefied natural gas mounted gas cylinder |
| CN109718849A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | Inactivate the regeneration method of hetero-atom molecular-sieve and the application of regenerated molecular sieve |
| CN111115652A (en) * | 2018-10-30 | 2020-05-08 | 国家能源投资集团有限责任公司 | Method for controlling crystal grain size of TS-1 molecular sieve and method for preparing small-grain TS-1 molecular sieve |
| CN112076782A (en) * | 2019-06-14 | 2020-12-15 | 大连理工大学 | Alkali metal ion modified titanium-silicon molecular sieve for propylene and hydrogen peroxide gas phase epoxidation reaction and preparation method thereof |
| CN117003255A (en) * | 2022-04-27 | 2023-11-07 | 中国石油天然气股份有限公司 | Tungsten-containing TS-1 molecular sieve and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4425672A1 (en) * | 1994-07-20 | 1996-01-25 | Basf Ag | Oxidation catalyst, process for its preparation and oxidation process using the oxidation catalyst |
| CN1102442C (en) * | 1998-04-10 | 2003-03-05 | 中国石油化工集团公司 | Preparation method for Ti-Si molecular sieve |
| ATE298626T1 (en) * | 1999-04-08 | 2005-07-15 | Dow Global Technologies Inc | METHOD FOR PRODUCING A CATALYST CONTAINING GOLD AND TITANIUM |
| WO2007126139A1 (en) * | 2006-04-27 | 2007-11-08 | Sumitomo Chemical Company, Limited | Method for producing epoxy compound |
-
2008
- 2008-03-20 CN CN2008101023058A patent/CN101537372B/en active Active
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9486790B2 (en) | 2011-10-31 | 2016-11-08 | Dalian University Of Technology | Modification method of titanium-silicalite zeolite based on the mixture of quaternary ammonium salt and inorganic alkali |
| CN103183356A (en) * | 2011-12-30 | 2013-07-03 | 中国石油化工股份有限公司 | Method for modifying titanium silicalite molecular sieve by precious metal source |
| CN103183356B (en) * | 2011-12-30 | 2015-03-18 | 中国石油化工股份有限公司 | Method for modifying titanium silicalite molecular sieve by precious metal source |
| CN107879355A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Modified with noble metals HTS and its preparation method and application and a kind of method of alkene direct oxidation |
| CN107879355B (en) * | 2016-09-30 | 2019-11-15 | 中国石油化工股份有限公司 | Modified with noble metals Titanium Sieve Molecular Sieve and its preparation method and application and a kind of method of alkene direct oxidation |
| CN109718849A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | Inactivate the regeneration method of hetero-atom molecular-sieve and the application of regenerated molecular sieve |
| CN109718849B (en) * | 2017-10-27 | 2023-04-11 | 中国石油化工股份有限公司 | Regeneration method of deactivated heteroatom molecular sieve and application of regenerated molecular sieve |
| CN107965661A (en) * | 2017-12-08 | 2018-04-27 | 芜湖市海格瑞德科技有限责任公司 | A kind of high stability liquefied natural gas mounted gas cylinder |
| CN111115652A (en) * | 2018-10-30 | 2020-05-08 | 国家能源投资集团有限责任公司 | Method for controlling crystal grain size of TS-1 molecular sieve and method for preparing small-grain TS-1 molecular sieve |
| CN111115652B (en) * | 2018-10-30 | 2021-08-13 | 国家能源投资集团有限责任公司 | Method for controlling crystal grain size of TS-1 molecular sieve and method for preparing small-grain TS-1 molecular sieve |
| CN112076782A (en) * | 2019-06-14 | 2020-12-15 | 大连理工大学 | Alkali metal ion modified titanium-silicon molecular sieve for propylene and hydrogen peroxide gas phase epoxidation reaction and preparation method thereof |
| CN117003255A (en) * | 2022-04-27 | 2023-11-07 | 中国石油天然气股份有限公司 | Tungsten-containing TS-1 molecular sieve and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101537372B (en) | 2011-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101537371B (en) | Modification method for titanium-silicon molecular sieve | |
| CN101274765B (en) | Noble metal-contained micropore titanium-silicon material and preparation thereof | |
| CN101537372B (en) | Modification method for titanium-silicon molecular sieve | |
| CN103183355B (en) | Precious metal modification method of titanium silicalite molecular sieve | |
| CN101658798B (en) | Method for modifying titanium silicate molecular sieve material | |
| CN101618338B (en) | Method for modifying titanium-silicon molecular sieve | |
| CN101618339B (en) | Method for modifying titanium-silicon molecular sieve | |
| CN101670298B (en) | Method for modifying titanium silicalite zeolite | |
| CN105854933A (en) | Modified titanium-silicon molecular sieve as well as modification method and application thereof | |
| CN101623653B (en) | Method for modifying titanium-silicon molecular sieve material | |
| CN101434587B (en) | Method for synthesizing epoxy styrene by catalytic oxidation of phenylethylene | |
| CN101654256B (en) | Method for in situ synthesis of titanium-silicon molecular sieve material containing noble metal | |
| CN101665256B (en) | Method for treating titanium silicate molecular sieve by using noble metal source | |
| CN101664696B (en) | Modification treatment method of titanium-silicon molecular sieve | |
| CN101658791B (en) | Post-treatment method of titanium silicate molecular sieve material | |
| CN101683984B (en) | Method for synthesizing titanium silicon materials containing noble metal | |
| CN103183356B (en) | Method for modifying titanium silicalite molecular sieve by precious metal source | |
| CN103183357B (en) | The modified with noble metals method of HTS | |
| CN101850267B (en) | Preparation method for precious-metal-containing titanium silicalite material | |
| CN101683986B (en) | Preparation method of titanium-silicon material | |
| CN101850266B (en) | Method for preparing precious metal-containing titanium silicalite | |
| CN101653734B (en) | Post-treatment method of titanium-silicon molecular sieve material | |
| CN101397240B (en) | Method for preparing p-dihydroxy benzene and pyrocatechol by phenol hydroxylation | |
| CN101670297B (en) | Synthetic method of titanium silicalite material containing noble metal | |
| CN101654255B (en) | Method for synthesizing titanium-silicon material containing noble metal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |