CN101664696B - Modification treatment method for titanium silicate molecular sieve - Google Patents
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- 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
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Abstract
The invention relates to a modification treatment method for a titanium silicate molecular sieve, which is characterized by comprising the following steps: adding the titanium silicate molecular sieve into an alkali source aqueous solution containing a protective agent and a noble metal source, and mixing the components evenly to obtain a mixture containing the following components in the ratio of the titanium silicate molecular sieve to the protective agent to an alkali source to the noble metal source to water of 100:(0.0001-5):(0.005-5):(0.005-10):(200-10,000), wherein the titanium silicate molecular sieve and the water are calculated in terms of gram, the protective agent and the alkali source are calculated in terms of mol, and the noble metal source is calculated in terms of noble metal elementary substance gram; and putting the obtained mixture into a closed reaction kettle to react under a condition of hydro-thermal treatment, and recovering and calcinating the product. Compared with the prior art, in an oxidation reaction such as the reaction for synthesizing propylene oxide through propylene epoxidation by using the titanium silicate molecular sieve, the selectivity, the catalytic activity and the stability of the oxidation reaction products are obviously improved.
Description
Technical field
The present invention relates to a kind of method of handling modifying titanium-silicon molecular sieve, a kind of method of more specifically saying so with modified with noble metals processing HTS, a kind of in other words conj.or perhaps through the synthetic method that obtains containing the noble metal titanium-silicon molecular screen material of modification.
Background technology
HTS is the novel hetero-atom molecular-sieve that last century, early eighties began to develop.The TS-1 that MFI type structure is arranged that has synthesized at present, the TS-2 of MEL type structure, the MGM-22 of MWW type structure and have than the TS-48 of macroporous structure etc.The synthetic titanium-silicon molecular sieve TS-1 of wherein Italian Enichem company's exploitation is that the transition metal titanium is introduced formed a kind of new titanium-silicone molecular sieve with good catalytic selectivity oxidation susceptibility in the framework of molecular sieve with ZSM-5 structure.TS-1 not only has the catalysed oxidn of titanium, but also has the shape effect selected and the advantages of excellent stability of ZSM-5 molecular sieve.Adopt the TS-1 molecular sieve as catalyst, can the polytype organic oxidizing reaction of catalysis, like the epoxidation of alkene, the partial oxidation of alkane, the oxidation of alcohols, the hydroxylating of phenols, the ammoxidation of cyclic ketones etc.Because the TS-1 molecular sieve is in organic oxidation reaction; Can adopt free of contamination low concentration hydrogen peroxide as oxidant; Oxidizing process complex process and problem of environment pollution caused have been avoided; Have unrivaled energy-conservation, economy of conventional oxidation system and advantages of environment protection, and have good reaction selectivity.
Hydrogen peroxide (H
2O
2) be the green oxidation agent of generally acknowledging, its oxidized byproduct has only water.Because H
2O
2Extremely unstable, meet heat, light, rough surface, heavy metal and other impurity can decompose, and have corrosivity, in packing, storage, transportation, will take special safety measure, therefore, with H
2O
2Production technology and use H
2O
2Downstream process combines, but these chemical products of ability more efficient use.
Many bibliographical informations have been arranged to load on Pt, Pd, Au and is used for original position on the titanium silicalite material and generates H
2O
2The research (like US 6867312B1, US 6884898B1 and " J.Catal., 1998,176:376-386 " etc.) of organic matter selective oxidation reaction.Appl.Catal.A:Gen., 2001,213:163-171 has reported that epoxidation propylene generates the research of expoxy propane (PO), H
2And O
2The reaction original position generates H on noble metal active positions such as Pd
2O
2Intermediate, the H that generates then
2O
2Intermediate is at contiguous Ti
4+Epoxidation propylene generates expoxy propane on the position, though reaction condition is gentle, selectivity is good, has defectives such as the lower and poor catalyst stability of catalyst activity.
CN1387948A discloses propylene to prepare epoxy propane catalyst in a kind of hydrogen-oxygen atmosphere, is with infusion process the compound loaded of palladium and platinum to be prepared difunctional palladium-platinum-titanium-silicon molecular sieve catalyst to HTS; Then the nano grade transition metal compound is mixed with the palladium-platinum-titanium-silicon molecular sieve catalyst of above-mentioned preparation, obtain palladium-platinum-transition metal-titanium-silicon molecular sieve catalyst system.
The CN1421389A disclosed method; Comprise the aqueous solution of silicon and the TS-1 molecular sieve that has synthesized according to molecular sieve (gram): Si (mole)=(70-1500): 1 mixed is even; The gained mixture was reacted 0.1-150 hour under 80-190 ℃ temperature in agitated reactor; Filter, wash and drying, the TS-1 molecular sieve that obtains with the silicon modification; The CN1245090A disclosed method; Comprise that TS-1 molecular sieve, acid compound and the water that will synthesize mix; And under 5-95 ℃, reacted 5 minutes to 6 hours, obtain 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 2 hours to the 8 day time of reaction, then with products therefrom filter, washing and dry.
Summary of the invention
The deficiency that the titanium silicalite material that the present invention is directed to noble metal loads such as Pt, Pd exists during as organic matter selective oxidation reaction catalyst; The compound that provides a kind of usefulness that is different from prior art to contain noble metal carries out the method that modification is handled to titanium-silicon molecular screen material, and modification gained HTS is used for the synthetic H of original position
2O
2The organic matter selective oxidation time, active high, good stability.
Method provided by the invention is HTS to be joined in the alkali source aqueous solution that contains protective agent and noble metal source to change hydrothermal treatment consists in the agitated reactor over to behind the mixing earlier; Reclaiming also, roasting promptly gets; More particularly this method is to join in the alkali source aqueous solution that contains protective agent and noble metal source HTS evenly mixed; Obtain consisting of HTS: protective agent: alkali source: noble metal source: water=100: (0.0001～5): (0.005～5): (0.005～10): the mixture of (200～10000), wherein HTS and water are in gram, and protective agent and alkali source are in mole; Noble metal source restrains in precious metal simple substance; Again with the gained mixture in closed reactor, after the reaction, reclaim product and roasting under the hydrothermal treatment consists condition.
In the modification processing method provided by the invention; The mixture composition is preferably HTS (gram): protective agent (mole): alkali source (mole): noble metal source (gram is in precious metal simple substance): water (gram)=100: (0.005～1): (0.01～2): (0.01～5): (500～5000).
Said HTS comprises the HTS of all kinds structure, like TS-1, TS-2, Ti-BETA, Ti-MCM-22, Ti-MCM-41, Ti-MCM-48 etc., is preferably TS-1.
Said protective agent is meant polymer or surfactant.
The derivative of polymer such as the said polymer such as glucose, cyclodextrin, polybenzimidazoles and polypropylene, polyethylene glycol, polystyrene, polyvinyl chloride, polyethylene is like derivatives such as the pyrrolidones of polymer, vinyl alcohol, ether, pyrimidines.With the polyethylene is example, as: polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl ethyl ether, polyethylene pyrimidine etc.Described polybenzimidazoles, polypropylene, polyethylene glycol, polystyrene, polyvinyl chloride, poly derivative are preferably their pyrrolidones, vinyl alcohol, ether or pyrimidine derivatives, and promptly described protective agent can be selected from polybenzimidazoles pyrrolidones, polybenzimidazoles alcohol, polybenzimidazoles ether, polybenzimidazoles pyrimidine, polypropylene pyrrolidones, POLYPROPYLENE GLYCOL, polypropylene ether, polypropylene pyrimidine, polyethylene glycol pyrrolidones, polyethylene glycol ether, polyethylene glycol pyrimidine, polystyrene pyrrolidones, polystyrene alcohol, polystyrene ether, polystyrene pyrimidine, polyvinyl chloride pyrrolidones, polyvinyl chloride alcohol, polyvinyl chloride ether, polyvinyl chloride pyrimidine, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl ethyl ether and polyethylene pyrimidine or the like.
Said surfactant can be anion surfactant, cationic surfactant and non-ionic surface active agent.
Anion surfactant such as soap, sulfuric acid, phosphate ester salt, alkylbenzenesulfonate, alpha-alkene sulfonate, alkylsulfonate, alpha-sulfo monocarboxylate, aliphatic acid sulfoalkyl ester, sulphosuccinates, alkylnaphthalene sulfonate, petroleum sulfonate, lignosulfonates, alkyl glyceryl ether sulfonate etc.
Cationic surfactant such as fatty amine quaternary cationics, ring-type cationic surfactant, softex kw, DDAO, three sufferings (ninth of the ten Heavenly Stems) ylmethyl chlorine (bromine) are changed ammonium.
Non-ionic surface active agent for example AEO, block polyoxyethylene polyoxypropylene ether, alkylolamides, polyol ester class, tween series, sapn is serial, fluorocarbon surfactant is serial.
Said noble metal source is selected from one or more noble metals, the organic matter that is preferably palladium and/or platinum or the inorganic matter in the noble metals such as Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au, can be other complex compound of oxide, halide, carbonate, nitrate, ammonium salt, sal-ammoniac salt, hydroxide or noble metal etc.With the palladium is example, and the palladium source can be inorganic palladium source and/or organic palladium source.Wherein inorganic palladium source can be other complex compound of palladium oxide, carbonate palladium, palladium bichloride, palladium nitrate, nitric acid ammonia palladium, sal-ammoniac palladium, palladium dydroxide or palladium etc., and the organic palladium source can be palladium, palladium acetylacetonate etc.
Said alkali source is inorganic alkali source and/or organic alkali source.Wherein inorganic alkali source is ammoniacal liquor, NaOH, potassium hydroxide, barium hydroxide etc.; Organic alkali source is urea, quaternary amine alkali compounds, fat amine compound, alcamine compound or the mixture be made up of them.
Said its general formula of quaternary ammonium base compounds is (R
1)
4NOH, wherein R
1For having the alkyl of 1～4 carbon atom, preferably propyl group.
Its general formula of said 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; The preferred fat aminated compounds is ethamine, n-butylamine, butanediamine or hexamethylene diamine.
Its general formula of said alcamine compound is (HOR
3)
mNH
(3-m)R wherein
3Be selected from alkyl with 1～4 carbon atom; M=1,2 or 3; The alcohols aminated compounds is MEA, diethanol amine or triethanolamine.
Said hydrothermal treatment consists condition is a hydrothermal treatment consists 2～360 hours under 80～200 ℃ of temperature and self-generated pressure; The process of said recovery product is well known to those skilled in the art; Do not have special feature; Generally include product filtration, washing, dry run, said roasting is handled more than 0.5 hour under 300～800 ℃ of temperature usually.
Method provided by the invention is improved the synergy of noble metal and HTS, the good dispersion of noble metal, and this has guaranteed its activity.Compare with prior art (like traditional dip loading technology), in oxidation reaction, for example in the reaction of epoxidation of propylene synthesizing epoxypropane, the selectivity of product and catalytic activity and stability obviously improve (seeing embodiment 12).
In addition, method provided by the invention increases the relative skeleton titanium amount of gained molecular sieve, and we adopt 960cm through investigating the infrared spectrum of material treated
-1Place's absworption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Characterize the relative skeleton Ti content in the HTS skeleton, judge the relative skeleton Ti content in the skeleton, be worth in the big more explanation skeleton that the skeleton Ti content is high more relatively, find out the sample that this method obtains, its I from table 1 according to the size of this value
960/ I
550Value is than the I of TS-1 and Comparative Examples
960/ I
550Value is big.
The specific embodiment
Following embodiment will do explanation further to the present invention, but therefore not limit the present invention.
Used reagent is commercially available AR among the embodiment.
Used HTS is by prior art Zeolites among Comparative Examples and the embodiment, 1992, and the synthetic TS-1 sieve sample of method described in the 943rd～950 page of the Vol.12.
Comparative Examples 1
The process of the conventional synthetic load type palladium/titanium-silicon molecular sieve catalyst of this Comparative Examples explanation.
With 20 gram titanium-silicon molecular sieve TS-1s and concentration be the 20m1 deionized water for stirring that joins of the nitric acid ammonia palladium complex solution 20ml of 0.01g/ml (in the palladium atom) evenly after, proper seal, temperature is at 40 ℃ of dippings 24 hours down.Air dry then, and in 300 ℃ of following hydrogen atmospheres, carried out reduction activation 5 hours, promptly get conventional load type palladium/titanium-silicon molecular sieve catalyst DB-1.
Sample skeleton infrared spectrum is measured (down together), KBr compressing tablet, test specification 400-4000cm on Nicolet8210 type Fourier infrared spectrograph
-1The I of DB-1
960/ I
550Data are listed in the table 1.
Embodiment 1
20 gram titanium-silicon molecular sieve TS-1s are joined in the TPAOH aqueous solution that contains nitric acid ammonia palladium complex and softex kw and mix; HTS (gram) wherein: softex kw (mole): TPAOH (mole): nitric acid ammonia palladium complex (gram is in palladium): water (gram)=100:0.2:0.05:0.02:600.Put into the stainless steel sealed reactor then; Hydrothermal treatment consists is 48 hours under 150 ℃ temperature and self-generated pressure; Gains are filtered, use water washing, after the air dry, and under 180 ℃, continued dry 3 hours; Roasting is 1 hour in 750 ℃ of following air atmospheres, promptly gets the titanium silicalite material A that handles through noble metal.I
960/ I
550Data are listed in the table 1.
Embodiment 2
20 gram titanium-silicon molecular sieve TS-1s are joined to contain in palladium bichloride and the polyacrylic sodium hydrate aqueous solution and mix; HTS (gram) wherein: polypropylene (mole): NaOH (mole): palladium bichloride (gram is in palladium): water (gram)=100:0.01:1.2:1.0:3500.Put into the stainless steel sealed reactor then; Hydrothermal treatment consists is 24 hours under 180 ℃ temperature and self-generated pressure; Gains are filtered, use water washing, after the air dry, and under 110 ℃, continued dry 3 hours; Roasting is 8 hours in 450 ℃ of following air atmospheres, promptly gets the titanium silicalite material B that handles through noble metal.I
960/ I
550Data are listed in the table 1.
Embodiment 3
20 gram titanium-silicon molecular sieve TS-1s are joined in the TPAOH aqueous solution that contains sal-ammoniac palladium complex and TTAB and mix; HTS (gram) wherein: TTAB (mole): TPAOH (mole): sal-ammoniac palladium complex (gram is in palladium): water (gram)=100:0.04:1.0:4.0:1200.Put into the stainless steel sealed reactor then; Hydrothermal treatment consists is 48 hours under 150 ℃ temperature and self-generated pressure; Gains are filtered, use water washing, after the air dry, and under 180 ℃, continued dry 3 hours; Roasting is 6 hours in 550 ℃ of following air atmospheres, promptly gets the titanium silicalite material C that handles through noble metal.I
960/ I
550Data are listed in the table 1.
Embodiment 4
20 gram titanium-silicon molecular sieve TS-1s are joined in the potassium hydroxide aqueous solution that contains palladium acetylacetonate and glucose and mix; HTS (gram) wherein: glucose (mole): potassium hydroxide (mole): palladium acetylacetonate (gram is in palladium): water (gram)=100:0.9:1.8:0.1:4600.Put into the stainless steel sealed reactor then; Hydrothermal treatment consists is 24 hours under 180 ℃ temperature and self-generated pressure; Gains are filtered, use water washing, after the air dry, and under 110 ℃, continued dry 3 hours; Roasting is 4 hours in 650 ℃ of following air atmospheres, promptly gets the titanium silicalite material D that handles through noble metal.I
960/ I
550Data are listed in the table 1.
Embodiment 5
20 gram titanium-silicon molecular sieve TS-1s are joined in the butanediamine aqueous solution that contains acid chloride and Tween 80 and mix; HTS (gram) wherein: Tween 80 (mole): butanediamine (mole): acid chloride (gram is in palladium): water (gram)=100:0.09:0.4:2.0:2000.Put into the stainless steel sealed reactor then; Hydrothermal treatment consists is 120 hours under 120 ℃ temperature and self-generated pressure; Gains are filtered, use water washing, after the air dry, and under 150 ℃, continued dry 3 hours; Roasting is 5 hours in 500 ℃ of following air atmospheres, promptly gets the titanium silicalite material E that handles through noble metal.I
960/ I
550Data are listed in the table 1.
Embodiment 6
20 gram titanium-silicon molecular sieve TS-1s are joined in the TPAOH aqueous solution that contains sal-ammoniac palladium and neopelex and mix; HTS (gram) wherein: neopelex (mole): TPAOH (mole): sal-ammoniac palladium (gram is in palladium): water (gram)=100:0.5:0.1:4.8:2500.Put into the stainless steel sealed reactor then; Hydrothermal treatment consists is 240 hours under 90 ℃ temperature and self-generated pressure; Gains are filtered, use water washing, after the air dry, and under 120 ℃, continued dry 3 hours; Roasting is 5 hours in 600 ℃ of following air atmospheres, promptly gets the titanium silicalite material F that handles through noble metal.I
960/ I
550Data are listed in the table 1.
Embodiment 7
20 gram titanium-silicon molecular sieve TS-1s are joined in the n-butylamine aqueous solution that contains palladium bichloride and polyvinyl ethyl ether and mix; HTS (gram) wherein: polyvinyl ethyl ether (mole): n-butylamine (mole): palladium bichloride (gram is in palladium): water (gram)=100:0.005:0.5:3.0:1000.Put into the stainless steel sealed reactor then; Hydrothermal treatment consists is 120 hours under 120 ℃ temperature and self-generated pressure; Gains are filtered, use water washing, after the air dry, and under 150 ℃, continued dry 3 hours; Roasting is 5 hours in 500 ℃ of following air atmospheres, promptly gets the titanium silicalite material G that handles through noble metal.I
960/ I
550Data are listed in the table 1.
Embodiment 8
20 gram titanium-silicon molecular sieve TS-1s are joined in the TPAOH aqueous solution that contains nitric acid ammonia palladium and polystyrene pyrrolidones and mix; HTS (gram) wherein: polystyrene pyrrolidones (mole): TPAOH (mole): nitric acid ammonia palladium (gram is in palladium): water (gram)=100:0.15:0.01:2.5:1500.Put into the stainless steel sealed reactor then; Hydrothermal treatment consists is 240 hours under 90 ℃ temperature and self-generated pressure; Gains are filtered, use water washing, after the air dry, and under 180 ℃, continued dry 3 hours; Roasting is 3 hours in 700 ℃ of following air atmospheres, promptly gets the titanium silicalite material H that handles through noble metal.I
960/ I
550Data are listed in the table 1.
Embodiment 9
20 gram titanium-silicon molecular sieve TS-1s are joined in the triethanolamine aqueous solution that contains carbonate palladium and polyethylene glycol and mix; HTS (gram) wherein: polyethylene glycol (mole): triethanolamine (mole): carbonate palladium (gram is in palladium): water (gram)=100:0.05:1.5:0.2:800.Put into agitated reactor then, hydrothermal treatment consists is 320 hours under 130 ℃ temperature and self-generated pressure, and gains are filtered, use water washing; After the air dry; And under 140 ℃, continued dry 3 hours, roasting is 7 hours in 400 ℃ of following air atmospheres, promptly gets the titanium silicalite material I that handles through noble metal.I
960/ I
550Data are listed in the table 1.
Embodiment 10
20 gram titanium-silicon molecular sieve TS-1s are joined in the diethanol amine aqueous solution that contains palladium oxide and sorbester p17 and mix; HTS (gram) wherein: sorbester p17 (mole): diethanol amine (mole): palladium oxide (gram is in palladium): water (gram)=100:0.1:0.2:0.5:520.Put into agitated reactor then, hydrothermal treatment consists is 320 hours under 130 ℃ temperature and self-generated pressure, and gains are filtered, use water washing; After the air dry; And under 140 ℃, continued dry 3 hours, roasting is 5 hours in 550 ℃ of following air atmospheres, promptly gets the titanium silicalite material I that handles through noble metal.I
960/ I
550Data are listed in the table 1.
Comparative Examples 2
The process of the conventional synthetic load type palladium-platinum of this Comparative Examples explanation/titanium-silicon molecular sieve catalyst.
With 20 gram titanium-silicon molecular sieve TS-1s and concentration are the nitric acid ammonia palladium of 0.01g/ml (in the palladium atom) with each 10ml of nitric acid ammonia platinum complex solution joins 20ml deionized water for stirring evenly after, proper seal, temperature was flooded 24 hours down at 40 ℃.Air dry then, and in 300 ℃ of following hydrogen atmospheres, carried out reduction activation 5 hours, promptly get conventional load type palladium-platinum/titanium-silicon molecular sieve catalyst DB-2.I
960/ I
550Data are listed in the table 1.
Embodiment 11
20 gram titanium-silicon molecular sieve TS-1s are joined in the TPAOH aqueous solution that contains nitric acid ammonia palladium, nitric acid ammonia platinum and softex kw and mix; HTS (gram) wherein: softex kw (mole): TPAOH (mole): nitric acid ammonia platinum (gram; In platinum): nitric acid ammonia palladium (gram is in palladium): water (gram)=100:0.1:1.2:2.0:1.2:1800.Put into the stainless steel sealed reactor then; Hydrothermal treatment consists is 72 hours under 180 ℃ temperature and self-generated pressure; Gains are filtered, use water washing, after the air dry, and under 180 ℃, continued dry 3 hours; Roasting is 5 hours in 600 ℃ of following air atmospheres, promptly gets the titanium silicalite material K that contains two noble metals.I
960/ I
550Data are listed in the table 1.
Table 1
| Sample source | The sample title | I 960/I 550 |
| It is synthetic to press document | TS-1 | 0.685 |
| Embodiment 1 | A | 0.721 |
| Embodiment 2 | B | 0.718 |
| Embodiment 3 | C | 0.716 |
| Embodiment 4 | D | 0.712 |
| Embodiment 5 | E | 0.713 |
| Embodiment 6 | F | 0.709 |
| Embodiment 7 | G | 0.711 |
| Embodiment 8 | H | 0.708 |
| Embodiment 9 | I | 0.699 |
| Embodiment 10 | J | 0.698 |
| Embodiment 11 | K | 0.712 |
| Comparative Examples 1 | DB-1 | 0.677 |
| Comparative Examples 2 | DB-2 | 0.671 |
Visible by table 1, the sample I of the inventive method preparation
960/ I
550Value is than the I of TS-1 and Comparative Examples
960/ I
550Value is big, explains that the sample skeleton Ti content of the inventive method preparation is high.
Embodiment 12
Present embodiment embodiment and comparative example are used for hydrogen and have propylene gas-phase epoxidation reaction effect down.
Each 0.5 gram of sample of getting the foregoing description 1-11 and Comparative Examples 1,2 respectively joins in the epoxidation reaction container that contains 50 ml methanol; Feed propylene, oxygen, hydrogen and nitrogen; Form propylene-oxygen-hydrogen-nitrogen mixture atmosphere (mol ratio is 1:1:1:7); 60 ℃ of temperature, pressure 1.0MPa, the propylene air speed is 10h
-1Condition under, carry out the reaction that epoxidation generates expoxy propane (PO).
Table 2, table 3 provide respectively is optionally data of 2,12 hours propylene conversion of reaction and P0.
Can find out that from table 2 and table 3 activity that the present invention obtains sample obtains the activity of sample apparently higher than Comparative Examples, selectivity also increases to some extent, has stability of catalytic activity preferably simultaneously.
Table 2
| Sample source | Sample number into spectrum | Propylene conversion % | P0 selectivity % |
| Embodiment 1 | A | 5.5 | 94 |
| Embodiment 2 | B | 5.3 | 92 |
| Embodiment 3 | C | 5.0 | 91 |
| Embodiment 4 | D | 5.2 | 94 |
| Embodiment 5 | E | 4.8 | 93 |
| Embodiment 6 | F | 5.7 | 91 |
| Embodiment 7 | G | 5.3 | 92 |
| Embodiment 8 | H | 4.7 | 91 |
| Embodiment 9 | I | 5.6 | 92 |
| Embodiment 10 | J | 5.1 | 93 |
| Comparative Examples 1 | DB-1 | 2.6 | 89 |
| Embodiment 11 | K | 5.8 | 93 |
| Comparative Examples 2 | DB-2 | 2.7 | 88 |
Table 3
| Sample source | Sample number into spectrum | Propylene conversion % | P0 selectivity % |
| Embodiment 1 | A | 5.2 | 93 |
| Embodiment 2 | B | 4.9 | 91 |
| Embodiment 3 | C | 4.8 | 91 |
| Embodiment 4 | D | 4.9 | 93 |
| Embodiment 5 | E | 4.6 | 91 |
| Embodiment 6 | F | 5.4 | 92 |
| Embodiment 7 | G | 4.9 | 93 |
| Embodiment 8 | H | 4.5 | 92 |
| Embodiment 9 | I | 5.3 | 91 |
| Embodiment 10 | J | 4.7 | 92 |
| Comparative Examples 1 | DB-1 | 0.4 | 80 |
| Embodiment 11 | K | 5.6 | 92 |
| Comparative Examples 2 | DB-2 | 1.2 | 81 |
Claims (14)
1. the modification processing method of a HTS; It is characterized in that this method is to join in the alkali source aqueous solution that contains protective agent and noble metal source HTS evenly mixed; Obtain consisting of HTS: protective agent: alkali source: noble metal source: water=100: (0.0001～5): (0.005～5): (0.005～10): the mixture of (200～10000); Wherein HTS and water are in gram, and protective agent and alkali source are in mole, and noble metal source restrains in precious metal simple substance; Again with the gained mixture in closed reactor; After the reaction, reclaim product and roasting under the hydrothermal treatment consists condition, wherein said protective agent is selected from glucose, cyclodextrin, polybenzimidazoles; Perhaps the mixture of one or more in polypropylene, polyethylene glycol, polystyrene, polyvinyl chloride, the polyethylene perhaps is selected from anion surfactant, cationic surfactant or non-ionic surface active agent; Said alkali source is ammoniacal liquor, NaOH, potassium hydroxide, barium hydroxide, perhaps is one or more the mixture in urea, quaternary ammonium base compound, amine compound, the alcohol amine compound.
2. according to the process of claim 1 wherein that said HTS is selected from one or more the mixture among TS-1, TS-2, Ti-BETA, Ti-MCM-22, Ti-MCM-41 and the Ti-MCM-48.
3. according to the process of claim 1 wherein that said HTS is TS-1.
4. according to the process of claim 1 wherein that said noble metal source is selected from the oxide of Ru, Rh, Pd, Re, Os, Ir, Pt, Ag or Au, halide, carbonate, nitrate, nitric acid ammonia salt, sal-ammoniac salt, hydroxide.
5. according to the process of claim 1 wherein that said noble metal is selected from palladium and/or platinum.
6. according to the process of claim 1 wherein that said noble metal source is selected from palladium oxide, carbonate palladium, palladium bichloride, palladium nitrate, nitric acid ammonia palladium, sal-ammoniac palladium, palladium dydroxide, perhaps is selected from palladium or palladium acetylacetonate.
7. according to the process of claim 1 wherein that said its general formula of quaternary ammonium base compound is (R
1)
4NOH, R
1For having the alkyl of 1～4 carbon atom.
8. according to the method for claim 7, wherein said R
1Be propyl group.
9. according to the process of claim 1 wherein that its general formula of said amine compound is R
2(NH
2)
n, R
2Be selected from alkyl or alkylidene, n=1 or 2 with 1～6 carbon atom.
10. according to the process of claim 1 wherein that said amine compound is ethamine, n-butylamine, butanediamine or hexamethylene diamine.
11. according to the process of claim 1 wherein that its general formula of said alcohol amine compound is (HOR
3)
mNH
(3-m), R
3Be selected from alkyl, m=1,2 or 3 with 1～4 carbon atom.
12. according to the process of claim 1 wherein that said alcohol amine compound is MEA, diethanol amine or triethanolamine.
13., it is characterized in that said mixture consists of: HTS: protective agent: alkali source: noble metal source: water=100: (0.005～1): (0.01～2): (0.01～5): (500～5000) according to the method for claim 1.
14. according to the process of claim 1 wherein that said hydrothermal treatment consists condition is a hydrothermal treatment consists 2～360 hours under 80～200 ℃ of temperature and self-generated pressure.
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| US6555493B2 (en) * | 2000-12-07 | 2003-04-29 | Arco Chemical Technology, L.P. | Solid epoxidation catalyst and preparation |
| CN1421389A (en) * | 2001-11-29 | 2003-06-04 | 中国石油化工股份有限公司 | Ti-Si molecular sieve modifying method |
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| US6555493B2 (en) * | 2000-12-07 | 2003-04-29 | Arco Chemical Technology, L.P. | Solid epoxidation catalyst and preparation |
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