SA517382097B1 - Process for the Regeneration of a Titanium Zeolite Catalyst for Propylene Epoxidation - Google Patents

Abstract

The invention relates to process for the regeneration of a catalyst comprising a titanium containing zeolite as catalytically active material comprising a stage comprising introducing a feed stream comprising propene, hydrogen peroxide or a hydrogen peroxide source, and an organic solvent into a reactor containing a catalyst comprising the titanium containing zeolite, subjecting the feed stream in the reactor to epoxidation conditions in the presence of the catalyst, removing a product steam comprising propylene oxide and the organic solvent from the reactor, stopping introducing the feed stream, washing the catalyst with a liquid aqueous system and calcining the washed catalyst.

Description

Process for the Regeneration of a Titanium Zeolite Catalyst for Propylene Epoxidation Full Description BACKGROUND The present invention relates to a process for regeneration of a titanium zeolite catalyst comprising a titanium containing (Ti) titanium as an active material Ujes active material; with a reinvigorated catalyst; and a continuous process for the preparation of propylene oxide in previous years; Various titanium-containing zeolites useful in catalyzing organic reactions such as converting olefins into epoxides, for example, have been developed. International Application No. 55229/98 A1 discloses the production and further use of titanium-containing zeolites for epoxidation of olefins. Titanium-containing zeolites are of great interest in industry; In this context, economic and environmental considerations are highly relevant. Effective regeneration of these zeolites for subsequent reuse in organic catalysts is strongly preferred over their replacement with a new catalyst. GENERAL DESCRIPTION OF THE INVENTION European Patent No. 1 221 442 a1 discloses catalyst regeneration from titanium zeolite catalyst | 5 used in dalle olefins in an epoxide with the help of hydrogen peroxide (D11:0); Jails the process to carry out the epoxidation reaction 0 where the regeneration of the spent catalyst is carried out with the help of hydrogen peroxide in the presence of olefin danse; the epoxidation reaction continues and where the regeneration is achieved by reversing the direction of the hydrogen peroxide feed. Hydrogen peroxide is also a valuable starting material and thus difficult to process due abd to decomposition Gye ISA 000827/2005A1 discloses catalyst regeneration from titanium silicalite catalyst after a continuous propene treatment process Epoxide with the help of hydrogen peroxide. The catalyst is cyclically regenerated with the help of a cule of methanol solvent at

A temperature of at least 100 °C 0 Methanol is a 13-value organic compound that requires an expensive and time-consuming extraction process. After regeneration, the epoxide treatment must be restarted at a temperature EL compared to the new catalyst in IAP No. A1.

5 International Application No. 97a1 discloses the catalyst regeneration of titanium-containing molecular sieve catalyst where; After pretreatment of the spent catalyst with water or alcohol 001; The pretreated catalyst is thus brought into contact with a mixture comprising hydrogen peroxide; water; and alcohol. This process thus includes two obligatory and sequential steps in which the spent catalyst is brought into contact with two different solutions. in addition to"; The mixture containing peroxide must be treated

hydrogen; coll) and alcohol. “The object of the present invention is to provide a simple and economical catalyst regeneration process comprising a titanium-containing zeolite as the catalytically active material used in the epoxidation of olefins. The present invention further aims to provide a regenerative catalyst comprising a zeolite containing titanium as the active substance Gin Allg that can easily be reused in epoxidation of olefins. 5 therefore; The present invention relates to a process for catalyst regeneration comprising a zeolite containing titanium as the catalytic active material comprising (i) a stage comprising 0 continuous preparation of propylene oxide comprising (a) a feed stream input comprising two propylene oxide; hydrogen peroxide or source of hydrogen peroxide; 0 and an organic solvent in a catalyst containing reactor comprising titanium-containing zeolite as the catalyst active material; (2) subjecting the feed stream in accordance with (11) in the reactor to epoxidation conditions in the presence of the catalyst resulting in obtaining a reaction mixture comprising propylene oxide and the organic solvent; (3) removing a product stream comprising propylene oxide and the organic solvent from 5 (b) stop feeding the feed stream into the reactor; (c) flush the catalyst with a tliquid aqueous system

Stage (1) further includes repeating the sequence of steps (a) to (c) “times where” is an integer number equal to at least 1; A regeneration process further comprising (2) a stage comprising the calcination of the catalyst obtained from (c) after repeating the sequence of steps A) (c) several times; where the sequence of stages (1) to (2) ahem where ““ is an integer number equal to at least 1” where is optionally repeated in each iteration of the sequence of stages (1) to (2); similar or different. amazingly; according to the process according to the present invention; (Sa regeneration catalyst comprising Calg) containing titanium as a catalytic active material used for epoxidation of olefins by washing the catalyst with liquid aqueous system tg of step (c) of stage (1) at least once without subsequent calcination; where 0 after said washing the catalyst shows the same or at least substantially the same catalytic activity as a corresponding new catalyst already without the calcination step and where regeneration results can also be improved by calcination of the Bg catalyst of stage (2) after one or more Additional washing steps. Stage 1 Stage (1) of the present process comprising (5) continuous propylene oxide preparation comprising (a1) the introduction of a feed comprising two proteins; hydrogen peroxide or source of hydrogen peroxide; and organic solvent into a reactor containing the zeolite-containing catalyst (2) subjecting the feed stream according to (a1) in the reactor to epoxidation conditions in the presence of taal 0 resulting in a reaction mixture comprising propylene oxide and the organic solvent; (31) removing A product stream comprising propylene oxide and an organic solvent from the reactor; (b) stopping the feed stream from entering the reactor; (c) flushing the catalyst with a liquid aqueous system; stage (1) also involves repeating the sequence of steps (a) through (c) “times where « It must be 5 integers equal to at least 1. Step (A1)

The feed stream according to (A1) comprises propane; hydrogen peroxide or hydrogen peroxide source;

and organic solvent.

Hydrogen peroxide or hydrogen peroxide source

Both hydrogen peroxide and hydrogen peroxide source can be used as epoxidation agent 5 in the feed stream according to (1)f

In the case of using hydrogen peroxide, it is preferable to have hydrogen peroxide Ble over a solution

caqueous hydrogen peroxide solution, where the solution includes

Preferably over 30 to 750 wt. of hydrogen peroxide in relation to the total amount of water.

It is also possible that hydrogen peroxide was formed in situ in the reaction mixture from hydrogen

0 and oxygen 0 in the presence of a suitable catalyst or catalyst system eg in the presence of a titanium-containing zeolite additionally comprising one or more metals AL) or a titanium-containing zeolite and an additional catalyst containing one or more metals Noble, for example, carried on a suitable support such as charcoal, inorganic oxide, or a mixture of inorganic oxides.

For the preparation of hydrogen peroxide in the feed stream according to (f) 1) a process using an anthraquinone can be used. This process is based on the catalytic hydrogenation of an anthraquinone compound to form a corresponding anthrahydroquinone compound after reaction with oxygen to form hydrogen peroxide and subsequent extraction of the hydrogen peroxide that was formed.The cycle ends by re-hydrogenation of the once formed anthraquinone (gal) in the oxidation.

0 An overview of a process using anthraquinones is illustrated in “Ullmann's Encyclopedia of Industrial Chemistry”, 5 edition, volume 13, pages 447 to 456 as an alternative; Hydrogen peroxide can be obtained through anodic oxidation of sulfuric acid with simultaneous sublimation of hydrogen at the cathode to produce peroxodisulfric acid P06:0*0018011. Hydrolysis of peroxodisulfuric acid Nf forms peroxodisulfuric acid

5 and of 2 hydrogen peroxide and sulfuric acid; which is thus derived. In the alternative AT hydrogen peroxide can be obtained directly from the elements hydrogen and oxygen.

In the manner (Janie) hydrogen peroxide is used in the feed stream according to (17) the organic solvent. The organic solvents to be used in (A1) are basically all known solvents for this purpose. Organic solvents such as alcohols, nitriles, and mixtures of the above are preferred. Optionally also water Canis the organic solvent is chosen from a group consisting of methanol and acetonitrile more specifically Sasi » the organic solvent is acetonitrile Feed stream according to (A1) in general; Prepare the feed stream according to (A1) according to any possible method.Therefore, the feed stream in (A1) can be prepared by mixing a stream comprising the protein, a stream comprising 0 hydrogen peroxide or hydrogen peroxide source, and a stream comprising the organic solvent, which involves mixing sequential; gl mixing a stream comprising the protein with a stream comprising the organic solvent and mixing the resulting stream with a stream comprising hydrogen peroxide or a source of hydrogen peroxide. One equivalent of peroxide The hydrogen produced from a hydrogen peroxide source. 5 preferably »; Quad in molar excess is present in the feed stream according to (a1) with respect to the hydrogen peroxide or one of the hydrogen peroxide equivalents produced from the hydrogen peroxide source. Preferably the molar ratio of propene and hydrogen peroxide or one of the hydrogen peroxide equivalents produced from the hydrogen peroxide source in the feed according to (a) ranges from 1 to 1.6; more preferably from 1.1 to 1.55; more favorably from 1.2 to 1.5 more favorably 0 from 140 to 145 generally; The feed stream according to (A1) comprises propane; hydrogen peroxide or hydrogen peroxide source; The organic solvent is not limited to either components included in the feed stream. (Jul) The feed stream according to (A1) may also include one additional ingredient on YI (eg at least one potassium-containing salt) 5 potassium-containing salt

With regard to the chemical nature of at least one potassium salt; There are no particular limitations. Preferably at least one potassium salt is chosen from a group consisting of at least one inorganic potassium salt; One organic potassium salt on “JN” and combinations of at least one inorganic potassium salt and at least one organic potassium salt.

Preferred inorganic potassium containing salts include; cle is not limited to potassium halide compounds, Jia potassium halides, potassium chloride, potassium bromide, potassium nitrate, potassium nitrate, potassium csulfate, potassium hydrogen sulfate, potassium hydroxide hydroxide 0 Potassium perchlorate Potassium salts that contain phosphorus - such as gla potassium dihydrogen phosphate or dipotassium hydrogen phosphate or potassium phosphate potassium phosphate or compounds of potassium pyrophosphates (Jia) monobasic potassium pyrophosphate or 5 dibasic potassium pyrophosphate or tribasic potassium pyrophosphate or quaternary potassium pyrophosphate alkaline potassium pyrophosphate (turb 600)” or potassium etidronate compounds pot assium Jie etidronates monobasic potassium etidronate or dibasic potassium etidronate or tribasic potassium etidronate or basic ol tetrabasic potassium etidronate Potassium cyanate 00851010 Potassium oxides Potassium Jie oxides Potassium oxide (K20) potassium oxide or potassium peroxide

(K202) potassium peroxide or potassium peroxide (KO2) superoxide is preferred; Organic potassium salts include potassium hydrogen potassium bicarbonate ¢(K2COs) potassium carbonate potassium carbonate 5 aliphatic saturated

carboxylic acids such as monocarboxylic acids having preferably 1 to 6; more favorably from 1 to 5; more preferably from 1 to 4; Most preferably from 1 to 3 carbon atoms such as formic acid acetic acid propionic acid dicarboxylic acids having 5 preferably from 2 to 6» more preferably from 2 to 4 atoms (gS) as coxalic acid malonic acid acid 010016 csuccinic acid tartaric acid tricarboxylic acids in which Preferred from 6 to 10 creon atoms Jie citric acid or isocitric acid or proyan acid-1 2 3-tri-tricarboxylic propane-1,2,3- ctricarboxylic acid 0 or tetra-carboxylic acids p1a “6082:00. Preferably, an organic potassium salt is chosen from a group consisting of potassium salts of aliphatic saturated monocarboxylic acids with it preferably” dl 2 3 4 5 or 6 carbon atoms » Potassium carbonate; t potassium; potassium acetate; Potassium propionate » potassium carbonate » and potassium bicarbonate. more favourably; An organic potassium salt is selected from a group consisting of potassium formate

potassium acetate formate 00188810000 potassium carbonate; and potassium bicarbonate. Subsequently; The potassium-containing salt is preferably selected from a group consisting of at least one inorganic potassium salt selected from a group consisting of potassium hydroxide 0 Potassium halides Potassium nitrate Potassium sulfate cpotassium hydrogen sulfate potassium perchlorate potassium dihydrogen phosphate or dipotassium hydrogen phosphate or potassium phosphate potassium phosphate or potassium pyrophosphate compounds such as monobasic potassium pyrophosphate or to dibasic potassium pyrophosphate, tribasic potassium pyrophosphate, or tetrabasic potassium pyrophosphate; or

potassium etidronate compounds such as monobasic potassium etidronate, dibasic potassium etidronate, tribasic potassium etidronate, or potassium tetrabasic etidronate; at least one organic potassium salt selected from a group consisting of potassium salts of aliphatic monosaturated carboxylic acids having preferably 1 » 32 4 » 5 or 6 carbon atoms » potassium carbonate; potassium picrionate; and a combination of at least one inorganic potassium salts and at least one organic potassium salts. more favourably; The potassium-comprising salt is selected from a group consisting of at least one inorganic potassium salt selected from a group consisting of 0-dihydrogen phosphate, dipotassium hydrogen phosphate, or potassium dihydrogen phosphate hydroxide; potassium halide compounds; potassium nitrate; potassium sulfate » potassium hydrogen sulfate; potassium perchlorate; At least one organic potassium salt selected from a group consisting of potassium formate; potassium acetate; cpotassium propionate potassium carbonate; potassium bicarbonate; and a combination of at least one of at least one inorganic potassium salt and at least one organic potassium salt. particularly preferred; The potassium-containing salt is potassium dihydrogen phosphate; dipotassium dihydrogen phosphate; or potassium formate. Subsequently; If one potassium salt is used; The salt comprising potassium is most preferably potassium dihydrogen phosphate”; dipotassium dihydrogen phosphate; or potassium formate. if two or more 0 salts containing potassium are used; One potassium salt is potassium dihydrogen phosphate; dipotassium dihydrogen phosphate; or potassium formate. In respect of the concentration of potassium-containing salt in the feed stream; There are no particular limitations. preferably the concentration of the potassium-containing salt in the feed is at least 710; preferably in a range of 10 to 7100; preferably from 20 to 7100; More preferably 5 from 30 to 7100 more preferably from 40 to 7100 than the limit of solubility of the potassium-containing salt in the feed stream. The term "limit of solubility of a single potassium salt" relates to

less in the liquid feed” as used in the context of the present invention by concentrating the saturation of the potassium-comprising salt in the liquid feed” whereby by adding more of the potassium-comprising salt the concentration of the potassium-comprising salt does not increase as a dissolution product of the mixture and the salt-comprising begins to Potassium in the precipitation The solubility limit of the potassium-containing salt in the feed will depend on the composition of the mixture and the Jie conditions The temperature at which and the pressure under which the feed stream is supplied Determining the solubility limit of the potassium-containing salt in the mixture is easy and intuitive for the skilled who knows said conditions and said composition for a particular mixture.A simple procedure for evaluating whether the amount of potassium-containing salt added ef is of the solubility limit is to pass the feed stream before subjecting it to epoxidation conditions in (A2) through a filter and measure the 0 pressure drop across The filter If the pressure drop through the filter increases with time in the stream and potassium-containing salt is present in the filter when it is counted off the grid, the amount of potassium-containing salt is The additive is already above the solubility limit. preferably in (A1); The molar ratio of the potassium contained in the potassium-comprising salt with respect to the hydrogen peroxide or one of the hydrogen peroxide equivalents produced from the 5 hydrogen peroxide source included in the feed is in the range from 1:10x10% to 1500*10”:1. Preferably From 10*20 ?: 1 to 1:410x1300 more preferably From 10x30 °: 1 to 101000 *: 1. The molar amount of potassium contained in a potassium-containing salt relates to the total molar amount of potassium contained in all the potassium-containing salts used in (A1); If two or more potassium-containing salts are used. 0 also preferably in (a1); The molar ratio of potassium to hydrogen peroxide or an equivalent hydrogen peroxide produced from the hydrogen peroxide source in the feed is in the range from 1:10x10 to 10”5000:1; Preferably from 10*15": 1 to 0 ?*: 1 more preferably Sain than 10«"20 ?: 1 to 10«"1.500: 1 more preferably from 1%10x25:1 to 10“*”1:300?: ol more Saas than 10““30”: 1 to 5 10”1.000”: 1.

preferably The feed stream according to (A1) shall be free of ammonium dihydrogen phosphate. more favourably; The feed stream according to (A1) shall be free of ammonium phosphate; ammonium hydrogen phosphate and ammonium dihydrogen phosphate. More Shaan the feed stream is according to (1) WA of 1 cammonium carbonate ammonium chydrogen carbonate 5 ammonium dihydrogen phosphate ammonium dihydrogen phosphate 1 cammonium hydrogen phosphate 1 ammonium phosphate 1 cammonium hydrogen pyrophosphate 1 cammonium pyrophosphate chloride 1 ammonium chloride 1 nitrate Ammonium cammonium nitrate and acetate 1 ammonium acetate . more specifically Sas 0 The feed stream according to 1) f) is free of 1 ammonium salt . JS term relates of” as used herein at a concentration of a corresponding compound of 2 ppm by weight at most; preferably 1 ppm by weight over wl SY on the total weight of the feed. Preferably; the feed contains according to (a1) Sodium in molar ratio of sodium with respect to hydrogen peroxide or one of the peroxide equivalents hydrogen produced from the hydrogen peroxide source in the range from 10”1*:1 to 1:10x250% preferably from 10”5:1 to 10*50*:1. preferably; The mixture preferably does not include the feed stream according to (A1) sodium dihydrogen phosphate (B0A:11H11) dissolved most preferably neither dissolved sodium dihydrogen phosphate nor sodium dihydrogen phosphate (Na2HPO4) dissolved phosphate” more preferably neither dissolved sodium dihydrogen phosphate nor dissolved sodium dihydrogen phosphate nor sodium phosphate (NasPO4) dissolved. If the feed stream according to (1) also includes at least one salt comprising potassium, the liquid feed is preferably prepared by incorporating at least four individual streams. Preferably a water stream comprising at least one dissolved salt is combined containing potassium with a stream comprising propene; or with a stream comprising hydrogen peroxide or a peroxide source

hydrogen; or with a stream comprising an organic solvent; or with a mixed stream of two or three of these streams” preferably with a stream comprising hydrogen peroxide or a source of peroxide

hydrogen; or with a stream comprising an organic solvent; Or with a mixed stream of the above. A propane-containing stream may additionally include propane where more preferably 798 wt. on oJ more preferably at least 799 wt.' more preferably at least 799.5 wt.' more preferably Sami At least 799.9 wt. of current propane and propane. preferably The weight ratio of propane to propane in the stream is at least 7:3. For example; Commercially available propene can be used which can be Wel polymeric or chemically bonded propene. typical; Proteins that have a polymeric order

0 has a protein content in the range of 99 to 799.8 by weight and a protein content in the range of 2 to 21 by weight. Proene having a chemical order typically has a propene content in the range from 2 to 798 by weight and a propane content in the range from 2 to 78 by weight. preferably A stream with a propane content in the range of 99 to 799.8 wt and a propane content in the range of 0.2 to 71 wt is used.

(Sa 5) Prepare a stream containing hydrogen peroxide or a source of hydrogen peroxide according to each possible method. It is possible to obtain a stream containing hydrogen peroxide by converting sulfuric acid into peroxodisulfuric acid through oxidation Anodic oxidation with simultaneous sublimation of hydrogen at the cathode Hydrolysis of peroxodisulphuric acid then leads to peroxodisulphuric acid

0 monosulfuric acid peroxomonosulphuric acid to hydrogen peroxide and sulfuric acid which is thus obtained again. Hydrogen peroxide can be prepared from the elements as well. based on a particular preparation method; The current containing hydrogen peroxide can be; For example; aqueous or aqueous/methanolic hydrogen peroxide stream; Preferably an aqueous hydrogen peroxide stream. In case of using caqueous hydrogen peroxide content

5 The current for hydrogen peroxide is usually in the range from 3 to 785 wt.' preferably from 25 to 775 wt.' more preferably from 30 to 750 wt.; like who

0 to 740 wt or 35 to 745 wt 40 to 750 wt. preferably at least 725 wt» more preferably at least 730 wt; More preferably at least 735 wt. of a hydrogen peroxide comprising stream consisting of water and hydrogen peroxide. Preferred ranges from 30 to 780 wt, 35 to 775 wt, or 40 to 770 wt. to provide sufficient stability of the hydrogen peroxide during hydroextraction; preferably mainly pure water; Suitable stabilizing agents (sale) are added to the water, preferably Jan. Purified water is used. specially; Noteworthy are 65 strong inorganic acids and/or chelating agents according to preferred extraction processes 0; Small amounts of nitrates 0108888 and/or phosphates and pyrophosphates are added respectively; as stabilizing agents; either as acids or as sodium salts These stabilizing agents are usually added in such quantities that the crude aqueous hydrogen peroxide solution contains from 50 to 400 parts per million by weight of 000 000 cations per million; 100 to 700 ppm by weight phosphorus 5 calculated as phosphate (*004); and from 50 to 400 ppm by weight of nitrate anions in each case calculated for the hydrogen peroxide contained in the crude aqueous hydrogen peroxide solution. favorite tide range; For example; 50 to 200 ppm by weight or 50 to 100 ppm by weight of sodium cations » 100 to 500 ppm by weight or 100 to 300 ppm by weight of phosphorus and 50 to 200 ppm by weight or 50 to 100 ppm by weight of nitrate. In addition, other stabilizing agents can be used such as stannites such as sodium stannite (Na2Sn02) and/or corganic phosphonic acids, specifically gh organic diphosphonic acids. acids such as etidronic acid preferably; The aqueous hydrogen peroxide stream le contains sodium in molar ratio

(210x250 for sodium with respect to hydrogen peroxide in the range from 10”*1*:1 to 10x50:1:1 more preferably than 10”5 ?:1 to) In general; the molar ratio of water is not subject to to the organic solvent in the feed stream given in (A1) to any given constraints. Preferably specifically in the case of the organic solvent on SY is acetonitrile.” The molar ratio of water to organic solvent is 1 : 4 over 1 :5 more favorably in a range from 1 : 50 to 1 : 4; more preferably from 1 : 15 to 1 : 4.2 more favorably from 1 : 10 to 1 ( 17 ) catalyst Gis In general, titanium-containing zeolites used as catalytic active material can have a structure type “ACO” ABW according to the following three-letter codes: zeolitic framework structure 0 “AFY ¢AFX and damaged tuff AFN (AFI) AFN (AFI) AFN (AFI) AFN (AFI) AFN (AFI) AFN (AFI) AFN (ATV ¢ATS ¢ATO ¢ATN AMI ¢AST ¢APD ¢APC AGV ¢AHT “CGS” “CGF” CFI “CDO” CAS “CAN” BRE “(BPH (BOG) KL “BEC (BEA” BCT “EDI (EAB”) (DON “DOH” DFT “DFO ¢DDR” DAC “CZP” CON “CLO” CHI “CHA” GON (“GME” “GIU” GIS FRA (FER (FAU) MASK ETR ESV (ERI EPI <EMT 15 10L < LEV (LAU ¢KFI) JBW (WW IWR TW ITH ITE ¢ISV) IFR (HEU “GOO” MFS ¢<MMFI <MER “MEP” MEL “MEI ¢<MAZ <MAR) LTL “LTA EMEL” LOS “NON” NEES (NAT (NAB) tMWW (MTW (MTT <MTN) MTF “MSO ¢<MOR” MON “RSN (RRO” RON “RHO” PON “PHI (PAU (PAR 050 051” “OFF” OBW “(NPO” SFE “SBT” SBS (SBE (SAV (SAT)) SAS (SAO ) RWY (RWR (RUT “(RTH (RTE 0” TON “THO <¢TER ¢STT ¢STI” STF ¢SSY “SOD” SGT “SEN SFO” SFH “SFG Lightning” YUG “WEN” WEI “VSV” VNI “VFI” VET UTL “USI “UOZ <“UFI ¢UEI “TSC for Lad 3-codes or a combination of two or more of these framework architectures. <ZON “Atlas of Zeolite Framework Types”, 5% edition 5 Letters and their definitions are referenced. Elsevier, London, England (2001).

Titanium-containing zeolites preferably have a framework structure 1471 framework structure MEL 7 framework structure MWW or a combination of two or more of these framework structures; preferably MFT framework structure MFT framework structure MWW or MWW framework structure (more preferably MWW framework structure or MWW framework structure; titanium-containing zeolite is a zeolite known as “1-15” (titanium silicate- 1) (titanium silicalite-1) or 111/11777". Preferably; ang specifically if the titanium-containing zeolite is a titanium-containing MWW structure; the titanium-containing zeolite includes on one or more aluminum ¢(Al) aluminum boron ¢(B) boron zirconium (Zr) zirconium valium “(V) 0 neonium ¢(Nb) neobium tantalum ¢ (Ta) tantalum ¢(Cr) chromium Mo) molybdenum ("tungsten ¢(W) tungestin ¢(Mn) manganese iron ¢(Fe) iron quails ¢(Co) ) cobalt nickel ¢(Ni) nickel zinc ¢(Zn) zinc gallium ¢(Ga) germanium (Ge) germanium etdium (In) indium tin (Sn) tin lead (Pb) palladium ( Pd) palladium (Pt) platinum gold (Au) gold cadmium ¢(Cd) cadmium 5 preferably one or more boron" zirconium; valium; niobium; Tantalum » Chromium » Molybdenum » Tungsten » Manganese » Iron » Coilate » Nickel » Zinc; gallium; germanium; indium; tin; lead, palladium; platinum; gold; cadmium, more preferably zinc. The term 'framework type titanium zeolite 7101717 as used in the context of the present invention' referred to by Lind as 110417177 relates to a zeolite of MWW framework structure which contains titanium as an isomorphous substitution element in a zeolite framework. zeolitic framework Preferably; the zeolitic framework is mainly free of aluminum and mainly consists of silicon, titanium” and oxygen. Preferably” at least 799 by weight” more preferably at least 799.5 by weight” more Sms 799.9 by weight of at least 5% of a zeolite framework consisting of esilicon titanium and oxygen.

That each titanium type is not part of the MWW zeolitic framework The preparation of catalysts is described as a structure of type MWW containing titanium” in US Pat. No. 2007043226 1) specifically in Examples 3 and 5 therein. The content is not subject to MWW titanium zeolite titanium zeolite to any particular constraint. in a range of 0.1 to 75 wt.; more preferably from 0.2 to 74 wt.; more favourably from 0.5 to 73 wt. more favourably from 1 to 72 wt; Based on the total weight of the MWW framework type titanium zeolite thus; The present invention relates to the process as 0 described above; Cus the MWW framework type titanium zeolite included in the catalyst in (a1) contains titanium” calculated as elemental titanium; in an amount in the range of 0.1 to 5 by weight; preferably from 1 to 72 wt.; silicon; sly on the total weight of MWW framework type titanium zeolite plus titanium; MWW titanium cules can include at least 5 other elements other than titanium; silicon; and oxygen. in general; It is possible that at least one other element is a covalent substituent that is preferably part of the zeolitic framework structure MWW; At least one other element is not a covalent substituent. This other non-covalent substituent can be placed on the zeolite by; For example; spray process lah:50; wet 0 immersion process Jie pre-wetting process; or any suitable process (AT) Preferably, at least one other element shall be selected from a group consisting of aluminium; boron; zirconium; valium; niobium; tantalium; chromium; molybdenum; tungsten; manganese; iron; quails; nickel; zinc gallium; germanium; indium; tin; lead; palladium; platinum; gold; cadmium and a combination of two or more preferably of a group consisting of boron, zirconium, valium, niobium, tantalium, chromium-5, molybdenum, tungsten, ferromanganese Quails, nickel, gallium, germanium, indium, tin, lead, palladium, platinum, gold, cadmium, a combination of two

Or more. More specifically, Shuai MWW framework type titanium zeolite contains zinc as another element in addition to titanium; silicon; and oxygen. More specifically Shaan MWW framework type titanium zeolite contains zinc as a single other element in addition to titanium; silicon; and oxygen. more favourably; MWW framework structure titanium cules contain 0g zinc as a single AT element in addition to titanium; Silicon »and oxygen, as it consists of at least 799 by weight; more preferably at least 799.5 wt.; more preferably at least 799.9 wt. of silicon zeolite framework structure; titanium; and oxygen. More specifically, Sha in the case of the framework type 7 titanium zeolite containing zinc as a single other element; 799 wt. titanium; silicon; oxygen; This Framework Structure Type MWW Titanium Zeolite containing Zinc as AT Single Load Element is referred to as 7011177" Catalyst Type MWW Titanium Zinc 5 The zinc content of Titanium Zeolite Framework Type 80177157 is not subject to Preferably the MWW framework type titanium zepolite contained in the catalyst in (17) contains cB calculated as elemental zinc; in an amount in the range from 0.1 to 75 by weight; i preferably from 0.2 to 74 wt., more preferably 0.5 to 73 wt., more preferably 1 to 72 wt., based on the total weight of titanium zeolite of framework type MWW 0. Therefore, the present invention relates to the process as described above; Wherein MWW titanium zeolite included in the catalyst in (1) contains zinc; calculated as elemental zinc; in an amount in the range from 0.1 to 75 by weight; preferably from 1 to 72 by weight; Titanium zeolite is of MWW framework structure type. Therefore, it is preferable to have titanium-containing zeolites included in j the catalyst in (1) a MWW 5 framework structure incorporating zinc; and contains cali) calculated as elemental titanium; in an amount in the range from 0.1 to 75 wt.; preferably from 1 to 722 wt.; Based on total weight

titanium-containing zeolite” containing zinc; calculated as elemental zinc; in an amount in the range from 0.1 to 75 wt” preferably from 1 to 722 wt; Bly on Total Gis is a titanium containing zeolite. The catalyst in accordance with (11) comprising cule of titanium framework type 47777 may be composed of titanium zeolite of framework type 1417177 preferably consisting of a titanium-containing type MWW or MWW-containing on titanium and zinc as described. in these cases; The catalyst can be MWW-type titanium zeolite in the form of moldable zeolite powder; eg as granules; a small ball such as a small ball obtained by spray drying or by spray granulation; 0 anthropomorphic body; For example, (Jaa) the shape of a sphere; tablet; cylinder; wheel; STAR or BS to be preferred; The catalyst is prepared according to (A1); incorporating framework-type titanium zeolite (MWW preferably a titanium-containing MWW gill structure or a titanium-zinc type 7 gill” as a cast comprising MWW titanium zeolite preferably Preferably a titanium-containing MWW type structure or a titanium-zinc MWW type 5 structure; by appropriate mixing of MWW framework type titanium zeolite with at least one binder sale and and/or with at least one binder precursor and optionally at least one pore-forming agent and/or at least one plasticizing agent The moldings can be molded into every possible geometry such as strands; for example it has six oblong, triangular, ob) oval, or circular cross-section, stars, discs, spheres, hollow cylinders, etc. Examples of such binders are cmetal oxides such as, for example, silicon oxide silicon oxide (D58:0) » aluminum oxide ¢ (A1,03) aluminum oxide titanium oxide (D1:0) » + oxygen d zirconium (ZrO2) zirconium oxide or (MgO) magnesium oxide or clays or mixtures of two or SST of such oxides or mixed oxides of at least two of silicon; Aluminium; titanium; zirconium; 5 for magnesium; Thanks to silicon oxide. Jie pore-forming agent Medium pore-forming agent Jie polymeric vinyl compounds include polyalkylene oxides

polyalkylene oxides such as cpolyethylene oxides polystyrene polyacrylate compounds 0115 polymethacrylate compounds 00170600010186 polyolefins polyamide 05 compounds and polyesters 00176516:5. The composition of the paste also includes pasting agents, organic polymers, colalls, in particular, such as 5-carbohydrates such as cellulose, cellulose derivatives, such as methyl cellulose, starch, starch potato “potato starch plaster has: 2110076”; Polyacrylates 105 cpolymethacrylates polyvinyl alcohol calcohol polyvinyl pyrrolidone polyisobutene (isn) or polytetrahydrofuran 0:000780b0017100. The use of water; alcohols or glycols 0 or mixtures of the above; such as mixtures of water and alcohol; or water and die glycol eg water and methanol; or water and cethanol or water and cpropanol or water (plug pg glycol propylene glycol as pasting agents preferably the catalyst is used according to (1); as a mold having the shape of oil products preferably cast products having a length preferably from 1 to 10 millimeters; more preferably than 1 to 7 alle more preferably from 1 to 5 millimeters; and diameter preferably from 0.1 to 5 alle more preferably from 0.2 to 4 millimeters; more preferably from 0.5 to 2 millimeters. For the preferred catalyst according to (a1) comprising a structure of MWW gill containing titanium and zinc; it is preferred to use As long as this catalyst is in the form of a fine powder or in the form of a block; The mold preferably contains the said fine powder. 0 The said catalyst according to (a1) in the form of a fine powder; It has a MWW titanium-zinc construction; It is characterized preferably by the following parameters and forms; Which includes embodied blends having certain dependencies: 1. cmicropowder Particles of which have a value of 17710 of 2 μm on WIN Said micropowder comprises intermediate pores having a mean pore diameter (417/8) in the range of 5 2 to 50 nm as defined by the mercury (Hg) mercury scale according to German Industry Standards (DIN) Deutsche Industrie norm 66133; And it includes (le based on

On the weight of the fine powder » at least 795 by weight of a fine-porous zeolite material free from

Aluminum has a MWW structure containing titanium and zinc. It is understood that the value of 0710 specifies

According to reference Example 8 of International Application No. 117536/2013.

2. Fine powder according to Model 1; It has a value of 710 in the range from 2 to 5.5 μm

preferably from 3 to 5.5 µm.

3. Fine powder of Model 1 or 2 has a value of 0850 in the range from 7 to 25 μm

Optionally a value of 09790 in the range from 26 to 85 µm. It is understood that the values of 0750 and 1990

Determined according to reference Example 8 of International Application No. 117536/2013.

4 fine powder according to any of Forms 1 to 3; where medium pores have an average diameter of 0_pores (4V/A) in the range from 10 to 50 nm”ie preferably from 15 to 40 nm

fia more preferably from 20 to 30 nm; As defined by a pore scale

Zinc according to German industry standards 66133.

5. Fine powder of any of embodiments 1 to ─ additionally comprises medium pores

Having an average pore diameter (4V/A) in the range from greater than 50 nm The listed 5 medium pores preferably have an average pore diameter in the range from 0.05 to 3 μm

As defined by the mercury pore meter DI 66133.

6. fine powder in any of Forms 1 to 5; Where are the micropores of a structure of type MWW

They contain titanium and zinc and have an average pore diameter in the range of 1.0 to 1.2 nm.

As determined by nitrogen adsorption according to DIN 0 66135.

7. fine powder in any of Forms 1 to 6; ly de includes the weight of the powder (GB

at least 9 by weight; Preferably at least 799.7 wt of type MWW construction

Contains titanium and zinc.

8. fine powder in any of Forms 1 to 7; Wherein a structure of type MWW containing 5 titanium-zinc contains zinc in an amount from 1.0 to 72.0 by weight; Preferably from 1.2 to 71.9

by weight Calculated as zinc and based on the weight of a titanium-zinc MWW structure.

9. Fine powder according to any of Forms 1 to 8; where DIY MWW containing titanium and zinc contains titanium in an amount from 1.0 to 72.0 by weight; preferably from 1.2 to 8 wt.; Calculated as titanium and based on the weight of a MWW structure containing titanium and zinc.

10. Fine powder according to any of Forms 1 to 9; crystalline As determined by X-ray diffraction (XRD) analysis of (80 -/+7)10 on JI preferably (85 /+10) 7. It is understood that the crystallinity determines According to reference Example 10 of International Application No. 117536/2013.

1. Fine powder according to any of Forms 1 to 10; Includes, based on total powder weight

0 Exact and calculated as an element»; less than 70,001 wt.; preferably less than 70.0001 wt. of noble metal; preferably chosen from a group consisting of gold; silver; platinum; ca gay Ll) iridium ciridium 1 cruthenium osmium cosmium and a mixture of two or more of the above; more preferably chosen from a group consisting of gold; platinum; gold"; and a mixture of two or more of the above.

5 12. Fine powder of any of Forms 1 to 11; includes ede based on the total weight of the fine powder calculated as the “element”; less than 70.1 wt.; Preferably less than 70.01 wt. of boron.

3. Fine powder of any of embodiments 1 to 12 has an AES by mass in the range 80 to 0 g/mL.

14. Fine powder of any of Forms 1 to 13; shall be “spray powder preferably obtained or obtained by spray- drying .drying” furthermore; Said catalyst according to (11) in the form of a template, having a type 7 structure containing titanium and zinc, is preferably characterized by the following parameters and patterns, including

5 model combinations have specific dependencies:

1. template; comprises zeolitic material ANA microporous aluminum-free having a titanium-zinc MWW structure » said die preferably includes fine powder includes lo based on weight of powder flour; by weight of at least aluminium-free microporous zeolite having a Type MWW structure 5 containing titanium and zinc; Said die most preferably comprises fine powder in accordance with any of the fine powder embodiments 1 to 14 as described above; The mold also preferably includes one binder (od) preferably a silica binder

.silica binder mold according to pattern 1; It contains medium pores having an average pore diameter in the range of .2

0 4 to 40 nm. Preferably 20 to 30 nano jie as determined by a mercury pore meter according to DIS 66133.

3. The mold according to model 1 or 2 has crystallinity; As determined by 6-ray diffraction analysis; It is (55 -/+ 10)7 on oY) preferably in the range from ((55 to 75) -/+ 10) 7. It is understood that the crystallinity is determined according to reference Example 10 of International Application No. 117536/2013 .

5 4. Template according to any of Forms 1 to 3; It comprises fine powder in an amount in the range of 70 to 780 wt. and a silica binder in an amount of 30 to 720 wt.; Fine powder together with Bale forms a bond of silica 799 by weight minimum of mold; wherein the template has a concentration of silanol groups with respect to the total number of silicon atoms of 76 over OEY preferably 73 at most as determined by nuclear NMR

(NMR) magnetic resonance 20:5" MAS 1185. It is understood that the concentration of silanol groups is determined in accordance with Reference Example 3 of International Application No. 117536/2013.

5. template according to any of templates 1 to 4; It shall be a braid having a circular cross-section and diameter in

range from 1.5 to 1.7 mm and has a crushing force of 5 N on JY) preferably

in the range of 5 to 20 N' more preferably in the range of 12 to 20

(ign 25) The crushing strength is determined by the crush strength test machine

6585 according to the method as described in Reference Example 2 of International Application No. 3. 6». template according to any of templates 1 to 5; The :295-NMR spectrum of said template has six peaks at the following positions: Peak 1 at -98 -/+ ea X per million; peak 2 at -104 -/+ ea X per million; peak 3 at -110 -/+ ea X ppm; peak 4 at -113 -/+ ea X per million; peak 5 at -115 -/+ ea X ppm; 0 Peak 6 at -118 -/+ X ppm; where Bx any of the peaks is 1.5 preferably 1.0 (more Jamin 0.5 where Q defined as x 100 = © 10 + 47/21 +51 + a6])/a3 is 2.5 over the most; preferably 1.6 at most; preferably 1.4 over SEY 5 such that RH] is the sum of the peak areas of the peaks 1 25 and [m + ke[ut the sum of the peak areas of the peaks is 4 5; 65 and 3d is the peak area of peak 3. It is understood that these –Si NMR properties are determined by reference Example 4 of IS No. 3 . 7. Template according to any of Forms 1 to 6; It has a water absorption in the range of 3 to 78 wt.; 0 preferably from 4 to 77 wt. It is understood that the water absorption is determined by reference Example 6 of International Application No. 117536/2013. 8. Template according to any of Models 1 to 7” The infrared spectrum (IR) Cada of said template includes a band in the region of (3700 - 3750) -/+ 20 cm and a band in the region of (3670 - 3690) -/+ 20 cm where the intensity ratio of the band in an area of (3700 - 3750) is 5 + 20 cm" for a band in an area of (3670 - 3690) -/ + 20 cm is 1.5 on

most; Preferably 1.4 at most. It is understood that these infrared characteristics are determined by reference Example 5 of International Application No. 117536/2013. Furthermore it; There is a preferred process for preparing said catalyst according to (a1) in the form of a fine powder and/or a block; It has a MWW structure containing titanium and zinc; with the following parameters and models; Which includes embodiment mixtures having certain dependencies: 1. A process comprising (a) provision of a suspension containing aluminum-free, microporous zepolitic Bale having a titanium-zinc MWW structure; (b) subjecting the suspension given in (1) to spray drying to obtain a fine powder; 0 (c) optionally calcining the fine powder obtained in (b); where the fine powder obtained in (b) or ( c) Preferably in (c) is preferably the fine powder in accordance with any of the said fine powder models 1 through 14 as described above. Rigid in the range of 5 5 to 725 wt; preferably 10 to 720 wt; suspension preferably aqueous suspension. Titanium and zinc according to (a) on zinc in an amount from 1.0 to 72.0 by weight; preferably from 1.2 to 71.9 by weight” calculated as Zn and titanium by an amount from 1.0 to 72.0 by weight; preferably from 1.2 to 71.8 0 by weight; calculated as titanium Depending on the weight of a MWW titanium-zinc structure 4. Process according to any of embodiments 1 to 3 where in (b) a spray-apparatus ¢spray-apparatus is used preferably a spray tower -tower for spray drying suspension; Said appliance has at least one spray-nozzle, preferably at least one two-component nozzle. Said nozzle has a diameter in the range of 3.5 to 4.5 mm. 5 5. Process according to any of Forms 1 to 4; where in (b); a spray device is used; Preferably a spray tower for spray drying the suspension; The aforementioned device is operated with a nozzle gas that has a temperature

in a range of 20 to 50 °C; preferably 20 to 30°C; a drying gas having a temperature in the range of 250 to 350°C; preferably 275 to 325°C; Said nozzle gas is preferably an inert gas; more preferably a nitrogen hub; Said drying gas is preferably an inert gas; More preferably a nitrogen hub. 6. Process according to any of Forms 1 to 5; where in (c); The fine powder is calcined at a temperature in the range of 600 to 700°C for a period of 0.5 to 6 hours. 7. Process according to any of Forms 1 to 6; further includes (d) shaping the fine powder obtained in (b) or (c) into a mould; 0 (e) optionally drying and/or calcination of the mold obtained in (d). 8. Process according to Model 7 where forming according to (d) includes (fl) mixing the fine powder with a binder or sale a binder; Preferably a silica binder or silica binder precursor wherein the weight ratio of a MWW-type structure containing titanium and zinc contained in a fine powder to the silica contained in or resulting from the silica binder is in the range of 3: 7 to 1: 4; to obtain a mixture; (bb) Formation of the mixture obtained in (I) to obtain the mould; Said formation comprises preferably of subjecting the mixture obtained in (1) to ull from which aie preferably obtain strands having a diameter preferably in the range from 1.0 to 0 millimeters” more Preferably from 1.5 to 1.7 mm. » wherein the mixing is carried out in (a) for a period in the range from 0 to 15 minutes; preferably from 30 to 55 minutes; more Sasi from 40 to 50 minutes. Where in (d); no mesopore-forming agent is added 5 selected from a group consisting of polyalkylene oxides such as cpolyethylene oxides and polystyrene

Polyacrylates 0115 Polymethacrylates 00170600010186 Poly

01015 Olefins 01065 Polyamide Compounds and Polyesters

2. Process according to any of Forms 7 to 11 where in (e); The mold is dried at a temperature of

a range of 100 to 150 °C for a period in the range of 10 to 20 hours and calcined at a temperature in the range of 500 to 600 °C for a period in the range of 0.5 to

Two hours.

3. The process according to any of Forms 7 to 12 (also includes:

(f) subjecting the template obtained in (d) or (e); preferably in (e); to process

with water;

0 (g) optionally drying and/or calcining the water-cured mold; where the template obtained in (f) or (g); preferably in (g); It is preferably a template according to any of the mentioned template templates 1 to 8 as described above.

4. The operation according to Form 13; where in (and); Hydrotreating involves treating the mold with liquid water in an autoclave at reversible pressure at a temperature in the range of 100 to 200

5 °C; preferably 125 to 175°C; more preferably 140 to 150°C for 2 to 24 hours; Preferably 6 to 10 hours.

5. Process according to Forms 13 or 14; where in (and); The mold weight-to-water ratio is in the range of 0.02 to 0.08; preferably from 0.03 to 0.07» more preferably from 0.04 to 0.06.

0 16. Operation according to any of the forms 13 to 15; where in (g); The water cured mold is dried at a temperature range of 100 to 150°C for a period of 10 to 20 hours and calcined at a temperature of 400 to 500°C for a period of 1 to 3 hours.

7. Process according to any of Forms 7 to 16; The mold is not subjected to steam treatment.

5 in respect of said preferred process for preparing said catalyst in accordance with (a1) in the form of a fine powder and/or a block; incorporating a titanium-zinc MWW structure” described above from

through forms 1 through 17; A structure of type MWW containing titanium and zinc can be prepared on the basis of which the suspension is provided in Form 1. No)”; In all possible ways. For example, it is possible to prepare an aluminum-free microporous bale zepolitan having a titanium-containing MWW structure and to subject a titanium-containing MWW structure to an appropriate treatment to obtain a MWW-type containing titanium structure titanium and zinc. Furthermore it; It is possible to prepare an aluminum-free zeolitic material having a structure of type MWW and to subject the MWW to suitable dallas to obtain a structure of type MWW containing titanium and zinc where; For example; Both titanium and zinc are discreetly listed in 141717. Further; It is possible to prepare an aluminum-free zeolite having a MWW structure, where; During the synthesis of a frame of type <(MWW 0) titanium is inserted and the resulting material is subjected to a treatment suitable for zinc inclusion; or zinc is introduced and the resulting material is subjected to suitable dallas for titanium inclusion; or both zinc and titanium are incorporated. As follows: Perceived Methods for preparing a titanium-containing MWW-type structure “Processes as Described” can be mentioned for example (JE in US Patent No. 1+ or in “Hydrothermal Synthesis of a novel Titanosilicate with Wu et al. .MWW Topology”, Chemistry Letters (2000), pp. 774-775 5 Preferably, an aluminum-free zeolite having a MWW structure containing titanium is prepared in a first stage; A titanium-containing MWW matrix to a suitable treatment to obtain a titanium-zinc MWW matrix. Preparation of an aluminum-free zeolite material having a structure of type MWW containing boron (B-) (1) (2) deboronization of M n Structure of type MWW containing boron to obtain an aluminum-free zepolitic material having a structure of type MWW (3) Inclusion of titanium in MWW to obtain an aluminum-free zepolitic material having a structure of type MWW 5 containing on titanium; (iv) Preferably acid-treating a titanium-containing MWW structure;

(5) Subjecting a titanium-containing MWW structure to immersion in zinc to obtain a structure

Type MWW containing titanium and zinc.

preferably in phase (1); A boron-containing MWW structure is prepared from

During the process whose steps and preferred conditions are determined by the following models 1 to 28 and aspects

The corresponding dependency is defined as:

1. Aluminium-free boron-containing zeolite preparation process includes framework structure

7 m »incl

(a) Hydrothermal synthesis of a precursor of a boron-containing MWW structure from a mixture

water-containing synthesis; source of silicon; source of boron; model compound 141717 leads to 0 obtaining a lactobacillus precursor of type MWW containing boron in its mother liquor; solution

the mother has a pH higher than 9;

(b) adjusting the pH of the parent solution; obtained in (a) and containing a produced sabe

l MWW-type boron-containing structure; to a value in the range from 6 to 9;

(c) Separation of the precursor of a boron-containing MWW structure from the pH-adjusted oY solution obtained in (b) through filtration in a filter medium.

2. Process according to Model 1; where in (a); makes up at least 795 by weight; Preferably 799

wt. (most preferably JY) at least 799.9 wt. of the water-synthesis mixture;

Silicon source » boron source » and model compound.

3. Process according to the 1 or 2 model where in of) the silicon source is chosen from a group consisting of -0 fumed silica; colloidal silica; and a mixture of the above; Silicon is preferred

edly all silica more preferably ammonia-fixed silica the boron source is selected from

A group consisting of boric acid, borate compounds, boron oxide

coxide and a mixture of two or more of the foregoing; The source of boron is preferably borbic acid;

and model compound MWW selected from a group consisting of piperidine ©0106:010; hexamethylene imine 5 ion 7 10:17-hexamethylene-1”5-pentanediammonium

ion msmstmdsm samahm-1,5-obeta»at-11,11,1],117,117,11" hydroxide 1 4-bis(11-

¢1,4-bis(N-methylpyrrolidinium) butane coctyltrimethylammonium hydroxide cheptyltrimethyl-ammonium hydroxide chexyltrimethylammonium hydroxide NNN trimethyl-1-adamantyl-1 ammonium ¢N,N,N-trimethyl-1-adamantyl-ammonium hydroxide 5 and a mixture of two or more of the foregoing; The model compound for MWW is preferably piperidine. A The process according to any of Models 1 to 3 where in (a); The synthesis mixture contains a boron source; Calculated as elemental boron with respect to the silicon source; calculated as elemental silicon with a molar ratio in the range from 0.4:1 to 2.0:1; more preferably from 0.6:1 to 1.9:1 more preferably from 0.9:1 to 1.4:1 water in relation to the silicon source; calculated as elemental silicon; in a molar ratio in the range from 1:1 to 0:1<preferably from 3:1 to 25:1 more preferably from 6:1 to 20:1; the typical compound in relation to the source of silicon; calculated as elemental silicon; molar ratio in the range from 0.4:1 to 1:20 preferably from 0.6:1 to 1.9:1; More preferably from 0.9:1 to 1:1.4. 5. Process according to any of Forms 1 to 4 where in (a); Hydrothermal synthesis is performed at a temperature in the range from 160 to less than 180 °C; preferably 170 to 175°C; for a period of time in the range from 1 to 72 hours; preferably 6 to 60 hours; More Thums from 12 to 50 hours. 0 6. Process according to any of embodiments 1 to 5 where in of) hydrothermal synthesis Gia is performed at least with stirring. 7. Process according to any of Forms 1 to 6 where in (a); The synthesis mixture additionally contains “sale fissile material p5660108”; Preferably a sale zeolite incorporating a framework structure 7 more preferably a boron-containing zeolite incorporating a MWW framework structure 5 8. Process according to Model 7 where the synthesis mixture contains fissile material; For the silicon source; with a weight ratio in the range of 0.01:1 to 1:1; Preferably from 0.02:1

to 0.5:1; more preferably from 0.03:1 to 0.1:1; Calculated as a quantity of a substance

The fissile strength in kilograms relative to the silicon contained in the silicon source is calculated as DAI

Silicon oxide in kilograms.

9. Process according to any of Forms 1 to 8; where the pH of the parent solution obtained from (a) is higher than 10; preferably in a range of 10.5 to 12; on

More preferably from 11 to 11.5.

0. Operation according to any of Forms 1 to 9; where in (b); The pH of the solution is adjusted

The mother obtained in (a) to a value in the range from 6.5 to 8.5; preferably

From 7 to 8.

0 11. Operation according to any of the models 1 to 10; where in (b); The pH is adjusted by a method comprising ((a)dil) acid to the mother solution obtained from (a) containing a boron yielder having structure of type 247717 to which preferably Wis is added at least with flipping.

5 12. Process according to Pattern 11 where in (off) the addition takes place at a temperature in the range from 20 to 70 °C; preferably 30 to 65°C; Most preferably from 0 to 60 degrees Age 3. Process according to Model 1 or 12) where in (a); the acid is an inorganic cacid preferably the aqueous solution contains an inorganic acid.

0 14. Operation according to Model 13; Where the inorganic acid is chosen from a group consisting of phosphoric acid, sulfuric acid, hydrochloric acid, enitric acid, and a mixture of two or more of the above; The inorganic acid is preferably 5-lyin. process according to any of Forms 11 to 14; In addition, the method includes

5 (bb) Stir the mother solution to which acid has been added according to ol) where during (bb); No acid is added to the parent solution.

6. The process according to Form 15; where in (bb) » Stirring is done at a temperature in a range of

0 to 70°C; preferably 25 to 65°C; more preferably

From 30 to 60 degrees Celsius.

7. Process according to any of Forms 1 to 16; where in (b); The size of the particles contained in the mother solution is increased; mentioned by the value of 0710 < DVS0 and the corresponding 0790; to at least 72 percent;

Preferably 73 on oY) Most preferably at least 74.5 Wd for Dv10

to at least 72 percent; Preferably 73 over JY (most preferably at least 74.5).

For DV50 (and for at least 75 percent) preferably 76 over “Ji more preferably

At least 7 Lad belongs to 0790.

0 18. Operation according to any of the forms 1 to 17; where the pH-adjusted mother solution obtained from (b) has a solids content in the range from 1 to 710 by weight; preferably from 4 to 79 wt» more favourably from 7 to 78 wt; Based on the total weight of the pH-adjusted mother solution obtained from (b).

9. Process according to any of Forms 1 to 18; Where the mother solution is pH-adjusted

5 Obtained from (b) having a filtration resistance in the range from 10 to 50 MPa*sec/m » preferably from 15 to 45 MPa*sec/m » more preferably from 20 to 0 MPa* sec/m.

0. Operation according to any of Forms 1 to 19; Further comprising (d) the washing of the boron precursor having a structure of type MWW obtained from (c); preferably the filter cake obtained from (c); where washing is preferably done with water with -washing agent Jud 1. Process according to Model 20; where in (d); The filter cake obtained from (c) has a washout strength in the range of 10 to 50 MPa*sec/m; Preferably 15 to 45 MPa*sec/m” more preferably 20 to 40 MPa*sec/m.”

2. Process according to pattern 20 or 21 whereby washing is carried out until the conductivity of the filtrate reaches 300 µS/cm on SY preferably at most 250 µS/cm; Most preferably at most 200 μS/cm. 3. The operation according to any of Forms 1 to 22; It also includes

(e) drying of the boron-producing material having a MWW-type structure obtained from (c); preferably from (d)” at a temperature in the range from 20 to 50° gin preferably from 20 to 40°C; more preferably 20 to 30°C; wherein the drying is preferably effected by subjecting boron having a structure of type 14171577 to an Oe stream preferably a nitrogen stream.

0 24. Process according to any of embodiments 1 to 23 wherein the residual moisture in the boron precursor has a structure of type MWW obtained from (c); preferably from (d); more preferably than (e); in a range from 80 to 790 wt.; Preferably 80 to 5 wt.

5. Process according to any of forms 1 to 24; It also includes

5 (f) suspension preparation; preferably an aqueous suspension; containing boron having a structure of type MWW obtained from (c); preferably from (d); more preferably than (e) dag solids content in the range from 10 to 720 wt.; preferably from 12 to 718 wt.; more preferably from 14 to 716 wt.;

(g) Perform spray drying of the suspension obtained from (f) containing a boron-producing substance

ld 0 structure type 0417157 to obtain spray powder;

(h) Performs calcination of the spray powder obtained from (g) containing boron-producing material

having a structure of type MWW preferably at a temperature in the range of 500 to 700

degrees Celsius more preferably from 550 to 650°C; more preferably than

5 to 625°C for a period of time in the range of 1 to 24 hours; preferably

5. From 2 to 18 hours; more preferably from 6 to 12 hours; to obtain powder

Sprinkle consists of at least 799 wt» more preferably at least 799.5 wt of boron having a structure of type MWW 6. process according to Form 25 where in (h); Calcination is performed in a panne pattern preferably in a rotary calciner preferably at productivity in the range of 0.5 to kg spray powder per hour. 7. Process according to Form 25 or 26) wherein the crystalline degree of boron having a structure of type MWW contained in the spray powder obtained from (h) is at least (75 + 5) 7; preferably (80 + 5) 7 at least; as determined by X-ray diffraction 8. Process according to any of the embodiments 25 to 27 wherein the surface area of BET 10 of boron has a structure of type MWW contained in the spray powder which obtained from (h) is at least [25 300 g; preferably in the range from 300 to 2500 lb; as defined by industry standard [lady] 66131 preferably” stage (2) of through the process whose preferred steps and conditions are determined by the following models 1 to 7 and the corresponding dependencies as defined: 5 1. a zepolitan sale preparation process; These include (a) provision of a boron-containing zeolitic material having a structure of type MWW obtained under stage (1); (b) deboronization of MWW-type boron by treating boron with a MWW-type structure with a liquid solvent system resulting in boron having a MWW-type 0 deboron; Where the liquid solvent system is chosen from a group consisting of water; monohydric alcohols cpolyhydric alcohols and mixtures of two or more of the above; Whereas the aforementioned liquid solvent system does not contain an inorganic acid, an organic acid, or a salt of (Ga), the acid is chosen from a group consisting of hydrochloric acid, 5-sulfuric acid, nitric acid, phosphoric acid, and formic acid aes formic acid. ‏

cacetic acid cpropionic acid oxalic acid coxalic acid and tartaric acid 2. The process is according to model 11 where the liquid solvent system does not contain inorganic acid or organic acid or salt previously.

3. Process according to Model 1 or 2 in which the liquid solvent system is selected from a group consisting of water; methanol sill propanol ethane-1 2-diol cethane-1,2-diol cethane-1-2-diol ¢propane-1,2-diol cethane-1 3-diol ¢propane-1,3-diol propane-1» 2 3- propane- ¢1,2,3-triol and mixtures of two or more of the above; Preferably water.

4 process according to any of Models 1 to 3; Where the curing according to (b) takes place at a temperature in the 0 range from 50 to 125°C.

5. Process according to any of Forms 1 to 4; Where the treatment is carried out according to (b) for a period ranging from 6

to 20 hours.

6. Process according to any of Forms 1 to 5; Where processing is carried out according to (b) in at least two steps;

Where between the two processing steps at least; MWW is dried preferably at a temperature in the 5 range from 100 to 150°C.

7. Process according to any of Forms 1 to 6; It also includes

(c) Post-processing of the MWW obtained from (b) by a process including

(c.1) Separation of MWW from the liquid solvent system;

(c.2) Preferably drying the separated MWW; preferably by spray drying; 0 (C.3) optionally calcination of MWW obtained from (C.1) or (C.2); Preferably at

Blom degrees are in the range from 500 to 700 Asian degrees

With regard to stage (3); Preferably a suitable starting mixture is subjected to; Preferably a mixture

water; Contains MWW and a titanium-containing precursor; preferably log contains

At least one suitable micropore-forming agent for hydrothermal crystallization at reversal pressure. It is possible to use fissile material

At least one occasion. as a suitable titanium-containing product material; Tetraalkyl compounds can be mentioned

tetraalkylorthotitanates such as tetrabutyl orthotitanate

For example. as a suitable micropore-forming agent; 010010106 Piperidine may mention hexamethylene imine or mixtures of piperidine and hexamethylene imine <hexamethylene imine (pe

For example. Preferably, the crystallization time is in the range of 4 to 8 days; on about

More preferably 4 to 6 days. during hydrothermal synthesis; The crystal mixture can be stirred. The temperatures applied during crystallization are preferably in the range from 160 to 200 °C; Most preferably from 160 to 180 degrees. after hydrothermal synthesis; Complete

Separation of the crystalline zeolite material obtained with a structure of type MWW containing

on titanium preferably from the mother liquor. All conceivable ways of separating a structure from type

MWW 0 contains titanium from its parent solution. These methods include; For example, Jd filtration methods, culturefiltration, diafiltration, and centrifugation, or for example, jill, spray drying processes, and spray granulation. A combination of the two can be applied. or more of these methods, according to the present invention

Separation of a structure of MWW gill containing preferably titanium from its parent solution through

5 Filtration to obtain a filter cake preferably subjected to washing; Preferably with water. after that; The filter dough is subjected to; Optionally further processing for

suitable hanger to spray drying or to ultrafiltration. Before separating a structure of type MWW containing

on titanium from its parent solution; It is possible to increase the content of a titanium-containing MWW structure in the parent solution by concentrating the suspension. if washing is applied; It is recommended to complete the washing process

0 until the water wash has a conductivity of less than 1000 μS/cm; more preferably less than 900 μSm/cm; more preferably less than 800 μSm/cm; Most preferably less than 700 μS/cm. After separating a titanium-containing MWW structure from its parent solution (preferably achieved by filtration and after washing), the washed filter cake containing a titanium-type MWW structure preferably was subjected to drying

25 advance; For example by subjecting the filter cake to a suitable gas stream; preferably a nitrogen stream of duration preferably in the range of 4 to 10 hours;

Most preferably 5 to 8 hours. after that; The dried filter cake is pre-dried

preferably at temperatures in the range 100 to 300°C; more on

preferably from 150 to 275°C; More preferably 200 to 250°C

In a suitable atmosphere Jie nitrogen hub » air; or light air; Preferably in air or air

light. This drying can be achieved; (JB) by spray drying. after drying;

A titanium-containing MWW structure can be calcined at temperatures in a range

ranges from 500 to 700°C; more preferably from 550 to 675 °C;

more preferably from 600 to 675 °C in a suitable atmosphere such as nitrogen fumes; air;

or light air; Preferably in air or light air. Preferably calcination is not performed gis 0 (3).

Preferably » stages (3) and (4) are conducted through the process whose steps and conditions are determined

Preferred by the following models 1 through 27 and their corresponding dependencies as defined:

1. Process for preparing a titanium-containing zeolitic material having a MWW framework structure comprising

0) Provide the MWW deboronated crystalline zeolite obtained 5 according to stage (2);

(b) Inclusion of titanium in the zeolite material which is given in (a) and which includes

(B.1) Preparation of a synthesis mixture (Sle) containing the zeolite material provided in (1); compound

Model MWW and source of titanium”, where the molar ratio of the model compound MWW with respect to

silicon; Calculated as silicon oxide and included in the zeolite material which is provided in (a); 0 is in the range from 0.5:1 to 1.4:1;

(B.2) Hydrothermal synthesis of a titanium-containing zeolite having a MWW framework structure

from the aqueous synthesis mixture prepared in (b.1); This gives solution A

which includes the titanium-containing zeolite material having a MWW framework structure

(c) Spray drying of the mother solution obtained from (B.2) comprising titanium-containing zeolite 5 having MWW framework structure.

2. The process is according to the ol model where in (5.1); The model compound MWW is chosen from a group consisting of piperidine; hexamethyleneimine ion” eNeNeN 017:77” 17-hexamethyl-1; 5-pentanediammonium «N,N,N,N'.N' N'-hexamethyl-1,5-pentanediammonium ion 1 4-bis(17-methylpyrrolidinium (¢1,4-bis(N)butane) -methylpyrrolidini-um)butane 10 5-ammonium hydroxide coctyltrimethylammo-nium hydroxide 1-heptyltrimethylammonium hydroxide cheptyltrimethylammonium hydroxide 1-hexyltrimethylammonium hydroxide and a mixture of the two More than ever; be the compound

Model 111717 preferably piperidine. 3 Operation according to Model 1 or 2; Where in (B.1); The source of titanium is selected from a group made up

0 ctetrabutyl orthotitanate ctetraisopropyl orthotitanate ctetra-ethyl orthotitanate ctitanium dioxide tetrachloride 01010H; ctitanium tert-butoxide and a mixture of two or more of the foregoing; The preferred source of titanium is tetrabutyl orthotitanate

4. Process according to any of Forms 1 to 3; where in the aqueous synthesis mixture in (b.1); molar ratio of titanium; calculated as titanium oxide and contained in the titanium source” in relation to silicon; Calculated as silicon oxide and included in a zeolite material having a molar ratio of boron oxide (B203) boron oxide silicon oxide at most 2:11 being in the range from 0.005:1 to 0.1:1; preferably from 0.01:1 to 0.08:1; more preferably

0 from 0.02:1 to 0.06:1.

5. Process according to any of Forms 1 to 4; where in the aqueous synthesis mixture in (b.1); molar ratio of water to silicon; Calculated > silicon oxide contained in a zeolitic material having a boron oxide: silicon oxide molar ratio of at most 0.02:1; They are in the range from 8:1 to 11 20 preferably from 10:1 to 18:1 more preferably Sm 5 from 1:12 to 1:16.

6. Process according to any of Forms 1 to 5; where in the aqueous synthesis mixture in (b.1); molar ratio of the model compound MWW with respect to silicon; Calculated as silicon oxide and included in the zeolite material which is provided in (1); be in the range from 0.5:1 to 1.7:1; Preferably from 0.8:1 to 1.5:1 more preferably from 1.0:1 to 1.3:1.

7. The process according to any of the forms 1 to 6 where in (B.2); Hydrothermal synthesis is performed at a temperature in the range of 80 to 250 °C; preferably 120 to 200°C; more preferably from 160 to 180 degrees gia 8. the process according to any of forms 1 to 7 where in (B.2); Hall hydrosynthesis is performed for a duration in the range of 10 to 100 hours; more preferably from 20 to 80 hours;

0 is more preferable from 40 to 60 hours.

9. The process according to any of forms 1 to 8 where in (B.2); Hydrothermal synthesis is performed in a closed system at reversible pressure.

0. Operation according to any of Forms 1 to 9; where not during (b.2); not after (b.2) and before (c); The titanium-containing zeolite having a MWW framework structure is separated from its parent solution.

5 11. Process according to any of Forms 1 to 10; where the mother liquor subjected to (c) comprising the titanium-containing zeolite having a MWW framework structure has solids content; optionally after concentration or dilution; in a range from 5 to 725 wt.; more preferably from 10 to 720 wt.; Based on the total weight of the mother liquor comprising the titanium-containing zepolite.

0 12. Process according to any of embodiments 1 to 11 where during spray drying in (c); The drying gas inlet temperature is in the range of 200 to 350°C and the drying gas outlet temperature is in the range of 70 to 190°C.

3. Process according to any of Forms 1 to 12; where the zeolitic material having a framework structure MWW obtained from (c) has a content of :5 in the range from 30 to 740 wt.; calculated

5 as elemental silicon » total organic carbon content (TOC) in

range from 0 to 214 wt.; titanium content from 2.1 to 72.8 wt.; Calculated elemental titanium; in all dlls based on the total weight of the zeolite material. 4. The operation according to any of Forms 1 to 13; Also included are (d) dallas the titanium-containing zeolite having a MWW framework structure obtained from (3) with an aqueous solution having a pH of at most 5. 5. The process according to Form 14, where after (c) and before (d); The spray-dried titanium-containing zeolite having the MWW framework structure obtained from (c) is not subjected to calcination. 6. Operation according to Form 14 or 15; where in (d); The weight ratio of the aqueous solution in relation to the titanium-containing zeolite 0 having a MWW framework structure is in the range from 10:1 to 30:1< preferably from 15:1 to 25:1; more preferably from 18:1 to 1:22 7. Process according to any of the forms 14 to 16; where in (d); The aqueous solution includes an inorganic acid; preferably selected from a group consisting of phosphoric acid; sulfuric acid; 5 HCl» tetraic acid; a combination of two or more of the above; The aqueous solution preferably includes tetraic acid. 8. Process according to any of Forms 14 to 17; where in (d); An aqueous solution has a pH in the range from zero to 5; preferably from 0 to 3; more preferably from 0 to 2.0 19. Process according to any of the embodiments 14 to 18 (where in (d) the titanium-containing zeolite having a MWW framework structure is treated with aqueous solution at a temperature in the range of 0 to 175°C; preferably 70 to 125°C; more preferably 95 to 105° Age 0. Process according to any of Models 14 to 19, where in (d); the zeolitic material is processed 5 titanium-containing MWWs having a framework structure MWW in aqueous solution for a duration in the range from 0.1 to 6 hours; preferably from 0.3 to 2 hours' more dus from 0.5 to 1.5 hours.

1. The operation according to any of Forms 14 to 20; where shal processing according to (d) takes place in a closed system

in reflex pressure.

2. The process according to any of Forms 14 to 21 also includes:

(e) Separation of the titanium-containing zeolite material with MWW framework structure obtained from (d) from the aqueous solution; Optionally, this is followed by washing of the separating zeolite containing

Titanium which has MWW framework structure

3. Process according to Model 22 wherein (e) comprises drying of the separated zepolitan and optionally

Titanium-containing washers having MWW frame construction

4. The process according to any of Forms 14 to 23 also includes:

0 (f) suspension preparation; preferably an aqueous suspension containing the titanium-containing zeolite having a MWW framework structure obtained from (d); Preferably (e) said suspension shall have a solids content preferably in the range of 5 to 725 by weight; more preferably from 10 to 720 wt.; Bl on the total weight of the suspension; and subject the suspension to spray drying.

5 25. The process is according to Model 24 where during drying oil the temperature of the drying gas inlet is in the range from 200 to 330 degrees Celsius and the temperature of the drying gas outlet is in the range of 120 to 180 degrees Celsius.

6. The process according to any of Models 14 to 25 also includes (g) the calcination of the titanium-containing zeolite having a framework structure MWW obtained

0 on it from (d); preferably than (e); more preferably than (and); The calcination is preferably carried out at a temperature in the range of 400 to 800°C; more preferably from 600 to 700 degrees Age 27 Process according to Form 26; where in (7) the calcination is carried out in a continuous pattern; preferably at a rate in the range of 0.2 to 2.0 kg of zeolite material per hour; more

5 preferably from 0.5 to 1.5 kg of zepolitan per hour.

according to stage (5); A structure of type MWW containing the obtained titanium is subjected

Preferably according to stage (4) to a suitable zinc treatment to obtain a structure of type MWW

It contains titanium and zinc used to prepare the suspension according to (a). in general; regarding (5);

There are no particular limitations ddan) that MWW-type construction contains titanium and zinc is preferred

The above specification can be obtained from the preferred zinc and titanium content. as most preferred; Stage (5) includes at least one suitable immersion stage; More preferably an immersion stage

Wet at least one. Regarding this immersion stage; It is preferable to contact with MWW structure

preferably containing titanium as obtained in accordance with (4) with a precursor containing

at least one suitable zinc in at least one suitable solvent (immersion in the wet state);

0 as most preferably water. as a suitable zinc-containing precursor; Zinc salts are particularly soluble in water; Cua zinc acetate dihydrate is the most preferred over the counter

particular. It is also preferable to prepare a solution of a precursor containing zinc; preferably an aqueous solution; and suspending a MWW-type structure containing titanium in this solution. like that

preferably »; immersion is performed at elevated temperatures; relative to room temperature; on

5 Preferably in the range of 75 to 125°C; more preferably 85 to 5°C; of duration preferably in the range of 3.5 to 5 hours; More preferably 3 to 6 hours. It is preferable to stir the suspension while immersing. After immersion a structure of Type 77 containing titanium and zinc preferably obtained is separated from the suspension. maybe

Depicted are all methods for separating a MWW structure containing titanium and zinc from a suspension. on about

0 preferred especially » shal is separated by filtering methods; Filtration (HU) dilution or centrifugal filtration. A combination of two or more of these methods may be applied. According to the present invention;

Separation of a MWW structure preferably containing titanium and zinc from suspension through filtration to obtain a filter cake preferably subjected to washing; Preferably with water. if washing is applied; It is preferable to continue the washing process until the washing with water has a conductivity of less than

5 1000 μSm/cm; more preferably less than 900 μSm/cm; more preferably less than 800 μSm/cm; Most preferably less than 700 μS/cm.

after that; Preferably the washed filter cake is subjected to pre-drying; For example by subjecting the filter cake to a suitable gas stream; preferably a nitrogen stream; of duration preferably in the range of 5 to 15 hours; more preferably from 8 to 12 if a structure of type MWW containing titanium or a structure of type MWW containing titanium lly is used as the catalytically active material of the present invention” the organic solvent being preferably acetonitrile. acetonitrile as Say dale Preparing the preferred catalyst with a structure of type MWW containing titanium and zinc according to specific data as disclosed in International Application No. 117536/2013a2 attached herein in full for reference. Titanium-1 silicate catalyst silicalite-1 catalyst According to the present invention, a titanium silicate-1 catalyst, preferably a titanium silicate-1 fixed bed catalyst, can be used as a catalyst.Titanium silicate-1 is a microporous zeolite having a structure of type MFI does not contain aluminum and where silicon 5 (4) in Wha silicate latex is replaced by titanium as titanium (4).The term “micropores” on gail used in the context of the present invention relates to pores having a pore size smaller than 2 nm Specified in accordance with DIN 66134. Tite silicate zeolite can be prepared Anium-1 by basically catalyst through any method possible. Typically at least one titanium zeolite of invention Jal is synthesized in hydrothermal systems 0 comprising a combination of an active silicon oxide source and a titanium source; such as ctitanium oxide with at least one model compound capable of forming the desired titanium zeolite in an aqueous suspension; For example in a basic suspension Blasi .000008 organic models are used. Ciately the synthesis is carried out at elevated temperatures; For example temperatures in the range from 150 to 200°C; 5 preferably from 160 to 180 degrees angle.

on the principle; Any suitable compound can be used as the silicon oxide source. Typical sources of silicon oxide include silicates silica hydrogel ¢silicic acid colloidal silica fumed silica ctetraalkoxysilanes ¢silicone hydroxides Precipitated silica and clays Both what is known as 'wet processing' for silicon dioxide and 'dry processing' for silicon dioxide can both be used. Preferably, where the particle size of silicon dioxide, for example, is in the range from 5 to 100 nm and the surface area of particles of silicon dioxide (at 0 cels) is in the range of 50 to 500 0 g.. Colloidal silicon dioxide is supplied; other; Ultrasil® (Hi-Sil® aul Glad Tokusil® “Valron-Estersil®” Santocel® “Vulcasil®” or Nipsil® “dry processing” of silicon dioxide is offered commercially among others; as Cab-O- (Reolosil® ¢Aerosil® Fransil® “Sil® 5” or ©Let's be with you. It is well known within the scope of the present invention that the use of a silicon dioxide-producing compound as a source of silicon oxide may be mentioned. For example, “tetra compounds” Jie ctetraalkoxysilanes e.g. tetraethoxysilane or ctetrapropoxysilane (Slaw) as product compound. As model Any suitable model may be used to provide the desired MFI zeolite structure. Specifically dag; ctetrapropylammonium hydroxide more preferably ctetra-n-propylammonium hydroxide 1-tetra-n-propylammonium hydroxide in a preferred embodiment of the process according to the invention; the pore-forming agent is removed forming agent in at least one step through calcination, as described below. Titanium silicate-1 in batches in an autoclave so that the reaction suspension is subjected to a pressure of 5 hours or several days until titanium silicate zeolite is obtained. According to a preferred embodiment of the present invention, the synthesis generally proceeds at elevated temperatures where

Temperatures during step hydrothermal crystallization are typically in the range of 150 to 200 °C; preferably in the range of 160 to 180 °C. normally the reaction takes place for a duration in the range of sae to several hours cold preferably for a duration in the range of 12 hours to 8 hours; More preferably 20 to 30 hours. AS can add 5 seed crystals to .synthesis batches

According to the embodiment of the invention “Jal,” the crystalline titanium-1 silicate obtained by filtration is separated from the creation suspension, that is, from the parent solution; Optionally wash and dry. All known methods can be used to separate crystalline titanium-1 silicate from a suspension. in between

Others » Filtration methods should be mentioned Ultrafiltration » Dilute filtration and centrifugation.

0 In the case of washing the obtained crystalline titanium-1 silicate, the mentioned washing step can be shal with any suitable washing agent; like; For example; water; alcohols; such as (JB) methanol; ethanol” or “methanol and propanol” or “ethanol and propanol” or methanol and ethanol and proyanol; or mixtures of water and at least one alcohol; such as; for example “water and ethanol” or “water and methanol” or water and ethanol + or cater ester and isroyanol or water and methanol and ethanol or water

methanol and proyanol; or water, ethanol, and propanol, or water, ethanol, methanol, and propanol. Water or a mixture of water and at least one alcohol is used; preferably water and ethanol; As a wash substance, titanium-1 crystalline silicate is dried at temperatures »generally; in a range of 80 to 160 °C; preferably 90 to 145°C; specifically on

Preferably from 100 to 130 degrees Celsius. instead of the aforementioned diel methods of separation as »among other things; filtration methods; ultrafiltration; dilution and centrifugal filtration; Suspension can be subdued; according to an alternative model; also to spray methods; For example, spray granulation and spray drying. If the crystalline titanium-1 silicate is separated by the spraying method, the two separation steps can be combined

5, drying in one step. In this case; Either a reaction suspension like this or a concentrated reaction suspension can be used in addition; It is possible to add sale as well

suitable as eg at least one suitable binder and/or one pore-forming agent at the bottom of the suspension - either to such a reaction suspension or to the concentrated suspension - prior to spray drying or spray granulation. Suitable binders are described in detail below. As a pore forming agent all the pore forming agents described above can be used 0 in Ala spray drying suspension; Pore-forming agent can be added, if added, in two ways. the first; A pore-forming agent may be added to the reaction mixture prior to spray drying. however; Lind may add a portion of the pore-forming agent to the reaction mixture prior to spray-drying; So that the remainder of the pore-forming agent is added to the -spray dried material in the case of concentration of the Fy suspension to improve the content of titanium-1 silicate in the suspension; Concentration 0 may be achieved for example JE through evaporation; eg steaming under low pressure; or through filtration by mesh flow. likewise; The suspension may be concentrated by separating said suspension into calla whereby the solid contained in one of each of the fractions is separated by filtration through filtration methods; Filtration by dilution, ultrafiltration or centrifugation and suspended after washing step and/or optional drying step at Alea of suspension. Thus the obtained concentrated suspension can then be subjected to (il) methods such as for example spray granulation and spray drying. according to an alternative model; SS is achieved by separating at least one titanium zeolite from a suspension; optionally resuspend the titanium zeolite together with at least one suitable additive as already described above; Cus titanium cules can be subjected to at least one washing step 0 and/or at least one drying step before resuspension. The resuspended titanium zeolite can then be applied to spraying methods preferably to spray drying. Spray drying is a direct method for drying slurries in suspensions or solutions by feeding a well-dispersed liquid-solid slurry as a suspension or solution; In addition, it often contains a binder; to an atomizer and then dried and proceeded in 5 streams of hot air. The winnowing medium can be one of several different types. The most common method is rotary winnowing, which uses the high-speed rotation of a wheel or disc to break slurry into droplets.

Step out of the wheel into the dig chamber to dry and flash it before ramming the chamber walls. Load winnowing can be achieved with single fluid firing nozzles that rely on hydrostatic pressure to push slurry through a small nozzle. Nozzles that fire multiple fluids (Lal) are used where gas pressure is used to push the slurry through the nozzle. The atomizer obtained using spray drying and spray granulation methods; Jie for example fluid bed drying; Solid and/or hollow spheres and can be largely composed of these spheres; The use of a rotary spray can also be envisaged Possible input temperatures for the carrier gas used are, eg, in the range from 0 200 to 600 °C, preferably in the range from 300 to 500 °C. for a carrier gas, for example Jha in the range from 50 to 200 °C. Mixtures of air; light air or oxygen-nitrogen with oxygen content up to 0 7 vol; preferably up to 5 7 vol; more preferably less than 5 7 vol; for example Jha up to 2 7 vol; as carrier gases 5 spraying methods can be made in upstream flow or upstream flow. preferably The titanium-1 silicate is separated from the reaction suspension through filtration or conventional centrifugation; optionally dried and/or calcined; and preferably re-suspend in cals an aqueous mixture of at least one binder and/or one pore-forming agent. The resulting suspension is then preferably subjected to spray drying or spray granulation. The obtained aerosol material can be subjected to an additional washing step; Said washing step is performed as described above. Optionally the washed and calcined sprayed material is then dried where drying and calcination is preferably carried out as described above. Under the cay model crystallization of the titanium-1 silicate takes place no sooner than the above described suspension is spray dried. Subsequently; A first suspension comprising a source of silicon oxide “preferably Di-5 silicon dioxide and a source of titanium oxide” is formed; The typical compound capable of forming

Ti-1 silicate. then; the suspension is spray dried; where then optionally an additional pore-forming agent is added to the spray-dried titanium-1 silicate. The spray-dried titanium-1 silicate obtained according to the above processes can be subjected to; Gj) to at least one wash. if at least one wash is performed; Preferably this should be followed by at least one drying step and/or calcination step. Titanium-1 silicate can be subjected; optionally obtained by spraying methods; further to at least one calcination step” which is performed according to a preferred embodiment of the invention after the drying step; or Ya from the drying step. At least one calcination step is performed at Sha 0 degrees generally in the range from 350 to 750 °C; preferably 400 to 700°C; specifically dag preferably from 450 to 650 degrees sie titanium-1 silicate may be calcined in any suitable gaseous atmosphere”; Air and/or light air is preferred. Furthermore it; The calcination processes are preferably carried out in a blast furnace; Rotary Cone and/or Belt Calcination Furnace “081” where calcination generally takes place for 5 hours or more; For example for a duration in the range of 1 to 24 or 4 to 12 hours. It is possible in the process according to the present invention; For example » calcination of titanium silicate - 1 time; twice or We in each case sad an hour at least; For example in every dls from 4 to 12 hours; preferably 4 to 8 hours; Where it is possible to keep the temperatures during the calcination step constant or to change the temperatures continuously or non-continuously. If calcination is done twice or Ble 0 the calcination temperatures in individual steps can vary or coincide. Subsequently; A preferred embodiment of the invention Jal relates to a process as described above; where the titanium-1 silicate separated by the filter is washed out of the suspension; for example through filtration or spray drying; with suitable detergent; And then subject it to at least one drying step. Drying takes place at temperatures »in general; in a range of 80 to 160 °C; preferably 90 to 145°C; Specifically dng preferably from 100 to 130°C. Mostly Samii after drying; calcination steps are performed. The step is made in degrees

temperature generally in the range from 350 to 750 degrees Celsius; preferably 400 to 700 degrees seminal; Specifically preferably from 450 to 650 agin degrees titanium silicate-1 may be used; which have been prepared as described above; dale directly as a catalyst in stages (1) and (3). However, it is particularly preferable to use a fixed bed catalyst in both phases (1) and (3); That is, the use of not the crystalline zeolite material in itself as a catalyst but the dsb material treated to give a template comprising titanium-1 silicate. Subsequently; according to a preferred model; A template comprising titanium silicate-1 is used; as described above; as a catalyst. in general; If template is used as a catalyst; Said catalyst may comprise all other possible compounds in addition to titanium-1 silicate according to the invention; For example; Among other things, at least one binder and/or pore-forming agent. Furthermore it; The catalyst may comprise at least one pasting agent in place of at least one binder and/or pore-forming agent or in addition to at least one binder and/or pore-forming agent. As a binder all compounds are suitable; This provides adhesion and/or cohesion between the titanium silicate-5 1 to be formed beyond physical adsorption that would occur without a binder. Examples of such binders are metal oxides; like; For example; silicon oxide; aluminum oxide; titanium oxide; Zirconium oxide, magnesium oxide, clays, or mixtures of two or more of these compounds. Clay minerals and natural or synthetic alumina compounds; similar For example (JE Ul beta-; cll clas ita-; LIS Shi- or theta-alumina and their inorganic or organic-0 metal compounds; (Ji) for example (Jal) gibbsite compounds are preferred cgibbsite cbayerite boehmite or pseudoboehmite or trialkoxyaluminates “trialkoxyaluminates ie for example” aluminum triisopropylate 1 on dag preferred as binders Of aluminum oxide. It is also preferred as a binder material, amphiphilic compounds, water with polarized and unpolarized moieties, and graphite. ¢montmorillonites; compounds of kaolin; ¢kaolins

5601001666 » Bentonite compounds challoysites cdickites compounds nacrites or anaxites . These binders can be used like this. It is also within the scope of the present invention to use compounds of which the binder is formed in at least one further step in the production of molds. Examples of such binders are ctetraalkoxysilanes ctetraalkoxytitanates tetraalkoxyzirconates or a mixture of two or more different bi alkoxysilanes or a mixture of two or more 8 different alkoxytitanates or a mixture of two or more different alkoxyzircones or a mixture of at least one tetraalkoxysilane and at least one tetraalkoxytitanate 0 or at least one tetraalkoxysilane and at least one tetraalkoxyzircone or at least one tetraalkoxytitanate At least one tetraalkoxyzircone or a mixture of at least one tetraalkoxysilane, at least one tetraalkoxytitanate and at least one tetraalkoxyzircone. In the context of the present invention binders comprising either US or Gia silicon oxide are preferred; 5 or which is Ble for sale producing silicon oxide; of which silicon oxide is formed in at least one further step to a greater degree precisely. in this context; Both colloidal ISL and what is known as 'wet cured' and what is known as 'dry cured' silica can be used. dng specifically preferably this silica is a amorphous silica with a particle size of silica, for example, in the range from 5 to 0 100 nm and the surface area of silica particles in the range from [50 to 2500] g Colloidal silica is preferably supplied as an alkaline and/or ammoniatic solution; more preferably as a Glas cammoniacal solution » among things al for example Nalco® «Syton® Ludox®S or Snowtex®. Wet cured silica (Glas) is provided. Among the coal items are for example 5096net “Vulcasil®” Ultrasil® Tokusil® “Valron-Estersil® < Santocel® 5 or # to sleep. Silica “dry cured” (Glas) is provided among “gyal” things for example “Cab-O-Sil®” “Reolosil® ¢Acrosil®S”

Fransil® i.e. © Let's Make It Kind. Among other things » an ammonia solution of colloidal silica is preferred in the present invention. Accordingly, the present invention further describes a die containing a catalyst as described above; Said mold comprises titanium-1 silicate as described above and additionally silicon oxide as a binder wherein the binder used in accordance with (1) is a binder comprising or forming silicon oxide. in general; Load titanium zeolite can be formed without the use of a binder. Subsequently; The present invention relates to a process; Where in phases (1) and (3); The titanium-1 silicate catalyst is obtained by forming the titanium-1 silicate to give a template comprising titanium-1 silicate and preferably at least one (dda) specifically a 0 silica binder. if it is good; At least one pore-forming agent may be added to a mixture of titanium silicate-1 and at least one binder or at least one binder; For further processing and to form a stereolithic body of the catalyst to be used as a fixed bed catalyst. The pore-forming agents that can be used are all compounds that; Regarding the produced template; Availability of a specific pore size and/or a specific pore size distribution of 5 and/or specific pore sizes. on dag select; availability of pore-forming agents; Regarding the produced template; micropores and/or micropores; Specifically dag medium pore and fine pore. Subsequently; The present invention relates to a process; Where in phases (1) and (3); The titanium-1 silicate catalyst is obtained by forming the titanium-1 silicate to give a template comprising titanium-1 silicate and preferably at least one “dda” specifically a 0 silica binder The template is specifically porous Fine and medium pore. For examples dle pore forming agents that can be used; The pore-forming factors already mentioned above are indicated. preferably The pore forming agents used in the molding process according to the invention are polymers that can be dispersed in suspension or emulsified in water or in aqueous solvent mixtures. It is particularly preferred as polymers of “fie polymeric vinyl compounds” eg 5; ¢polyalkylene oxides such as polyethylene oxides polystyrene polyacrylate compounds 017015 Polymethacrylate compounds

017010115 ¢polyolefins Polyamide 85 compounds and polyesters;+ carbohydrates; like; For example; Cellulose or cellulose derivatives ein eg (Jal) methylcellulose or sugars or natural fibers Suitable pore forming agents graphite of eg coll if size distribution is desired porous A mixture of two or more pore-forming agents may be used. 5 In a particularly preferred embodiment of the process according to the invention “as described below” the pore-forming agents are removed through calcination to give a solid body of a porous catalyst. preferably Specifically, pore-forming agents providing intermediate pores and/or at least one bond pore and titanium-1 silicate to form, preferably, medium pores; are specifically added to a mixture of

0 titanium silicate-1. in general; Lad-1 titanium silicate can be formed to obtain the solid body of the catalyst without the use of a pore-forming agent. Besides the binder and optionally a pore-forming agent it is also possible to add additional ingredients; eg Jia) at least one paste former; to the mixture formed to obtain the stereoscopic body of the catalyst.

5 if at least one paste-forming agent is used; Said paste-forming agent shall be used either in place of or in addition to at least one pore-forming agent. specially; Compounds that can also act as pore-forming agents can be used as paste-forming agents. The paste forming agents that can be used are all compounds known to be suitable for this purpose. preferably organic polymers; ang specifically affinity for water; cia for example; Cellulose derivatives

0 cellulose; like; For example; methylcellulose; we want quot; For example; potato starch for wallpaper adhesives » polyacrylate compounds; polymethacrylate compounds; polyvinyl alcohol; epolyvinylpyrrolidone is a polyisobutene or polytetrahydrofuran. The use of water can be mentioned; alcohols, glycols or BDA of the above; such as mixtures of water and alcohol; or water and glycol; such as for example water and methanol; or water and ethanol; or water and proyanol; or water

5 propylene glycol; as paste-forming agents. preferably cellulose is used; cellulose derivatives; water and mixtures of two or ST of these compounds; Jie water and cellulose or water and cellulose derivatives

as a paste-forming agent. In a specifically preferred embodiment of the process according to the invention; factor is removed

at least one paste formation through calcination; as described in more detail below;

to give the template.

According to the AT embodiment of the present invention, “sale” may add at least one acidic additive to the mixture being formed to obtain the template. if an acidic additive is used; Help yourself

Organic acid compounds that can be removed through calcination. In this context it can be mentioned

Cryoxylic acids ‎acids About us«08100»; (fis) for example (JU) formic acid

Oxalic acid [5] or citric acid antan. It is also possible to use two

or ST of these acidic compounds.

0 The order of adding the ingredients to the mixture formed to obtain the lage is not the same if, for example, a combination of binder is used; pore forming agent; a paste-forming agent and optionally at least one acidic compound; It is possible for each of Vil to add at least one binder and then one pore-forming agent on (JAY) at least one acidic compound and finally at least one paste-forming agent and alter the sequence with respect to at least one binder; 1 pore-forming agent

5 on BY) at least one acidic compound and at least one paste-forming agent. after the addition of at least one binder, at least one paste-forming agent, at least one pore-forming agent, and/or at least one acidic additive to a mixture comprising titanium-1 silicate; The mixture is typically homogenized for 10 to 180 minutes. among other things; Kneading agents edge mills or Gu extruders are used on dag

0 Select preferably for homogenization. The mixture is kneaded preferably. on the industrial level; Grinding in an edge mill is preferred for homogenization. homogenization is performed; as a rule; at temperatures in the range from about 10 °C to the boiling point of the paste forming agent and atmospheric or slightly higher atmospheric pressure. (Glad) At least one of the compounds described above can then be added. The thus obtained mixture is homogenized; preferably kneaded; until it is formed

5. Extrudable plastic material

The homogenized mixture is then formed to obtain a mould. All suitable known molding methods can be used; like extrusion; drying lh granulation by spraying; agglomeration” i.e. mechanical compaction with or without the addition of binder or additional spheroidizing material; That is, pressing through circular and/or rotational motions. The preferred forming methods are those where conventional extrusion agents are used to form a mixture comprising titanium-1 silicate. Subsequently; For example, extrusions with a diameter of 1 to 0 millimeters, preferably 2 to 5 millimeters, are obtained. In addition to using an extruder; Lad extrusion press can be used to prepare moulds. The shape of the molds produced according to the invention can be chosen as desired. specially; among other things; It is possible to form 0 balls.”; oval shapes; cylinders or discs. Similarly, hollow structures can be mentioned; For example, hollow cylinders, honeycomb structures, or even geometric shapes in the form of stars. Formation can occur at ambient pressure or at a pressure above ambient pressure” eg JE in a pressure range from 1 bar to several hundred units of bar. Furthermore it; mad can occur at or above ambient temperature” eg 5 in the temperature range from 20 to 300°C. If drying and/or calcination is part of the forming step, temperatures of up to 600°C can be envisaged. Bal Lage Fusion can occur under ambient or controlled atmosphere. court atmosphere; eg (JB) is an inert gas atmosphere (gas) in reducing atmospheres and/or oxidation atmospheres. The formation step is preferably followed by at least one drying step. This at least one drying step 0 is performed at temperatures in lai generally from 80 to 160° Agia preferably from 90 to 145°C and more specifically preferably from 100 to 0°C; usually sad 6 hours or FST for example in a range of From 6 to 24 hours However, depending on the moisture content of the material to be dried, it is possible to use smaller drying times such as, for example, about 1, 2, 3, 4 or 5 hours as well.

before and/or after the drying step; Preferably (Sa) fragmentation of the extrudate obtained e.g. cade. Preferably granules or flakes having a particle diameter of 0.1 to 5 millimeters are obtained; more precisely 0.5 to 2 millimeters; Hereby, according to a preferred embodiment of the present invention, drying of the molds is followed, respectively, preferably by at least one calcination step, calcining is carried out at temperatures generally in the range from 350 to 750°C, preferably from 400 to 700 °C, in particular preferably from 450 to 650 °C.Calcining may be carried out in any suitable gaseous atmosphere where air and/or light air is preferred.Furthermore, calcination is preferably carried out in a cmuffle kiln A rotary kiln and/or calcining kiln with belts, where the calcination Bae is generally 0 in the range of 1 hour or ST for example in the range of 1 to 24 hours or in the range of 3 to 12 h.in operation according to glial) it is possible according to that; For example; calcining the stereo body of the catalyst once; twice or more often in each case for at least an hour; like; For example » in each case within the range of 3 to 12 hours; The temperatures during the calcination step may remain constant or change continuously or intermittently. If shal 5 is calcined twice or (Ble) the calcination temperatures in individual steps can vary or coincide. According to a particularly preferred embodiment the catalyst solid is subjected to a hydrothermal treatment heat treatment can be performed hydrothermal by any suitable method known to those skilled in the art.Therefore, the catalyst or catalyst generally formed is brought into contact with water or water vapor.Typically said hydrothermal treatment is carried out by charging the catalyst or 0 according to the invention together with water in Autoclave heating the slurry to a temperature in the range of 100 to 200°C; preferably in the range of 120 to 150°C at a pressure in the range of 1.5 to 5 bar; preferably in the range of 2 to 3 bar Duration in the range of 1 to 48 hours, preferably in the range of 24 to 48 hours Typically followed by a single wash step on (BY) preferably with water as a wash After treatment 5 with water the catalyst is dried Preferably and/or calcined, whereby drying and calcination shall be performed as already described above. According to a preferred embodiment » hydrothermal treatment is carried out by stirring

the stereotactic body of the catalyst in an autoclave; Where the flip rate is set to a flip rate so that

Avoid friction wear as much as possible. The use of the catalyst in the form of cylindrical outputs; however;

Some frictional wear is required to obtain cylindrical outgrowths that have rounded edges. with Kun

These articulations have circular edges»; Higher mass densities can be achieved, for example to use metabolites

Pronunciation as a fixed-bed catalyst in an R1 tube reactor and/or in a reactor

It has shaft reactor 162. Moreover; The dust formation stimuli mentioned in

The epoxidation process in stages (1) and (3).

Furthermore it; In the epoxidation process of the present invention; A silicate catalyst is used

titanium-1 as described above; It has fine pores and medium pores; Includes from 49.5 0 to 280; preferably 69.5 to 780 by weight of titanium silicate-1; aly on the total

ral weight and from 19.5 to 750; Preferably from 19.5 to 730 by material weight

at least one bond; Preferably a silica binder based on total body weight

assembly of the catalyst.

If titanium-1 silicate is used as the catalytic active material according to Jall's invention the organic solvent is preferably methanol.

Step (2)

According to (2) the feed stream according to (11) in the reactor is subjected to epoxide treatment conditions in the presence of

The catalyst was obtained by obtaining a reaction mixture containing propylene oxide and the organic solvent.

The reactor used in (A2) may be operated in an isothermal or adiabatic manner; where 0 preferably the reactor in (a2) is Jolie operated under isothermal conditions.

appropriately The conversion rate of starting materials can be controlled by adjusting the temperature; the pressure

Weight Hourly Space velocity (WHSV) of starting materials; and the like.

For example JU the degree of the reaction sha can be set so that at least 790 of a factor is converted

Epoxide treatment. The amounts of starting material present in the reaction mixture before and after the peroxide-treated 5 reaction can be analyzed by any suitable technique; For example .chromatography

in general; The continuous epoxidation reaction in (A2) may be performed in any suitable vessel or reactor.

Ciately the reaction in (a2) is carried out in at least one continuously running Jolie Jie reactor

A tubular or tube reactor preferably containing at least one ripening jacket

surrounds at least one tube” in which the temperature of the reaction mixture is controlled evenly

Heat using a Jad medium Heat a cheat transfer medium preferably by passing a medium

Heat transfer through the reactor cap. If the reaction is carried out in (A2) in this reactor containing

at least one ripening cap; The term “dad heat of reaction of epoxidation curing” is specified on

Syntax used here as the temperature of the heat transfer medium prior to controlling the temperature of the reaction mixture; on

Preferably as a medium temperature the heat decreases at the inlet of the isothermal reactor 0

Preferably, at least one of the reactors where the reaction is conducted in accordance with (A2) is a reactor

Tubular or tube reactor.

(Sa) Use of a catalyst comprising a titanium-containing zepolite JS Possible image described

above; including powder; fine powder; preferably a spray powder; As a bar includes 5 powders; or as a mold containing a fine powder; Preferably a spray powder. preferably »

The catalyst comprising a titanium-containing zeolite is used as a template comprising powder or

fine powder preferably a spray powder; More preferably as a powder incorporating bar

flour Preferably a spray powder.

The catalyst used in step (21) of the present invention may be placed in the reactor in every possible manner. On the 0 towards ciate the catalyst is placed as a fluidized bed or as a fixed bed; more preferably

as a fixed layer.

preferably The conditions for curing the epoxide in (A2) include a curing reaction temperature

epoxide in the range from 20 to 100 °C; More preferably from 25 to 80

degrees Celsius more preferably from 25 to 60°C; Most preferably from 30 5 to 60 degrees Age

preferably The epoxidation conditions in (A2) include an epoxidation reaction pressure in the range from 5 to 100 JL most preferably from 10 to 32 bar; More preferably from 15 to 25 JL where the epoxidation reaction pressure is defined as pressure at the outlet of the isothermal reactor.

Thus the epoxidation conditions in (A2) preferably include an epoxidation reaction temperature in the range of 20 to 100 °C and an epoxidation reaction pressure being in the range of 5 to 100 bar more preferably an epoxidation reaction temperature in the range of 25 to 60 °C and epoxidation reaction pressure in the range of 10 to 32 bar more preferably epoxidation reaction temperature in the range of 30

0 to 60 °C and epoxidation reaction pressure in the range of 15 to 25 bar. The term 'epoxidation conditions' as used herein of the present invention relates to the epoxidation reaction in step (21) where for a proportion of 798 on (BY) preferably 799 on (J) more preferably at least 799.9 of The overall Jeli time Sha degree of reaction and pressure are in the ranges specified above. The term Jane' dell time as used 5 in the context of the present invention relates to the reaction time of a particular catalyst layer that is used prior to either being discarded or subjected to regeneration, specifically at the initiation of the V(A2) epoxidation reaction when the catalyst is fresh i.e. at the initiation of the V(A2) epoxidation reaction; the reaction temperature, pressure, or both can be outside the above mentioned Gaal for a short time from time. preferably The flow rate of the heat transfer medium is chosen such that the temperature difference between its input temperature and its output temperature is 3 K at most (more preferably 2 K over SY) more preferably Sais K at most. Preferably” the epoxidation reaction is carried out according to step (21) of the present invention at essentially a constant conversion of the epoxidation agent; preferably the conversion of hydrogen peroxide. Preferably, to determine the conversion of hydrogen peroxide the molar flow rate of hydrogen peroxide in a stream of The effluent removed in (A3); denoted herein is the molar flow rate of hydrogen peroxide in the feed stream supplied in (A1); denoted herein

K.:""; Whereas the hydrogen peroxide conversion is specified as 100 (mon/min—1) x preferably; The input temperature of the hypothermic medium described above is set in Gaull's preferred aforementioned to keep the hydrogen peroxide conversion essentially constant in a range of 80 to 7100 more preferably from 90 to 7100; more preferably from 95 to 7100; more favorably from 99 to 7100 more favorably from 99.5 to 7100; most preferably from 99.9 to 100 7. The term 'epoxidation conditions comprising' as used in the context of the present invention relates to the epoxidation reaction in step (a2) wherein for at least 8; preferably at least 799; More preferably at least 799.9 total reaction time; conversion of hydrogen peroxide is in the Gaal defined above. 0 term “total reaction time” as used in the context of the invention Jad) This relates to the reaction time that a particular catalyst bed is used prior to disposal Specifically at the initiation of the A2 epoxidation reaction when the catalyst is fresh i.e. at the initiation of the A2 epoxidation reaction the hydrogen peroxide conversion can be outside the aforementioned range for a short period of time. Preferably, the reaction temperature is not kept constant during the reaction but is adjusted continuously or gradually to allow a constant conversion of the hydrogen peroxide. Generally, as a result of inhibition of a particular catalyst, the reaction temperature is increased continuously or gradually. Preferably, the reaction temperature is increased continuously t or gradually by 1 K/day (K/day) at most” more preferably by less than 1 K/day. preferably The reaction mixture in the reactor is in (21) Sila under curing conditions 0 with an epoxide. Preferably (Junta) the reaction mixture consists of one liquid phase; of two liquid phases; or of three or more liquid phases. Preferably The reaction mixture in the reactor in (A2) consists of one liquid phase or, more preferably, two liquid phases of one liquid phase.In general, the reactor used in step (A2) of the present invention may be located horizontally or vertically.Preferably; The reactor is placed vertically. Preferably in the Gl positioned reactor the feed stream provided in (A1) may be passed in an up-flow mode or in a down-Jaw flow mode

mode 10 Top flow mode is preferred. preferably Ake in the direction of the feed stream flow; Heat-reducing medium is passed through the lid in a down-stream pattern. in general; The in(A2) epoxidation reaction may be carried out in one or more reactors which may be placed in parallel or in series. Preferably, the reaction in (a2) is carried out in one or at least two reactors; Preferably two consecutively placed reactors where between the two consecutively placed reactors suitable intermediate processing can be performed. If the reaction is carried out in two reactors placed in series, it is preferable to operate the first reactor as described above; That is, like a reactor operating under isothermal conditions; the second reactor is operational; that is, after the reactor; As an adiabatic reactor or mainly an adiabatic reactor. The term 'reactor' as used herein also includes two or more reactors laid in parallel whereby the passing feed stream is divided into two or more sub-streams; each sub-stream is passed into the reactor; and the effluent streams removed from the reactors are combined To obtain the total effluent stream, therefore, the epoxidation reaction can be carried out in at least one first reactor such as two or more first reactors, eg 2 3 4 first reactors placed in parallel which are preferably 5 isothermal reactors and in at least one second reactor such as two or more reactors (dull eg 2 3 4 of the second reactors; placed in parallel (Aly) preferably adiabatic or mainly adiabatic reactors if The epoxidation reaction was carried out according to (a2) in two sequentially placed reactors »preferably in the first reactor which is preferably the isothermal reactor« The 0 conversion of hydrogen peroxide Bll remains mainly in the range from 80 to 799; on preferably from 85 to 798; more preferably from 90 to 797 and in the second reactor designed in the manner of Junie as an aneothermal reactor or essentially an aneothermal Jolie; The entire hydrogen peroxide conversion becomes; i.e. the conversion of hydrogen peroxide taking into account the conversion in the first reactor and the second reactor; with a value greater than 799; preferably at least 799.5; more than 5 preferably 99.9 7 least. step (a3)

according to step (a3); A product stream comprising propylene oxide and the solvent is removed

organisms from the reactor. Said product stream is typically subjected to at least one processing step

To isolate propylene oxide from the product stream. Furthermore it; the organic solvent is subjected to; which includes

typical on the Lila products from the epoxidation reaction; preferably to one or more processing steps to allow recycling of the organic solvent; Preferably acetonitrile» eg

Preferred after one or more of the purification steps in step (a1). relay is described

The preferred processing steps are in Reference Example 2 and in Figures 1 and 2 below.

step (b)

according to (b); The feed stream input to the reactor is stopped in accordance with (A1).

0 is preferred; Step (b) further includes the separation of the reaction mixture comprising propylene oxide and the organic solvent from the catalyst comprising a zeolite containing titanium as the catalytic material. This reaction mixture may be separated from the spent catalyst comprising titanium zepolite by any suitable method; jie pumping discharge (all filtration; etc. optional; (b) also includes drying the catalyst prior to washing in (c); where preferably the catalyst is not dried before

5 The washing procedure in (c). if dried; Said drying preferably involves contacting the catalyst with a gas stream comprising nitrogen, preferably at a temperature of said gas stream in the range from 40 to 200 °C; more preferably in the range of 55 to 150°C; more preferably in the range of 70 to 100°C. Said separation can also be achieved by flushing the reactor with the organic solvent; Preferably nitrile gid.

0 therefore; in preferred form; The reactor is Jud to become WA of hydrogen peroxide; propylene and propylene oxide by replacing the feed stream according to (a1) with a stream consisting mainly of the organic solvent; preferably of acetonitrile until the reactor is essentially free of hydrogen peroxide; propylene, propylene oxide and optionally reactor decompression and degassing. For example; The stream is mainly composed of the organic solvent; Preferably from gid nitrile » contains

5 at least 760 wt.; preferably at least 770 wt» more preferably at least 5 wt» more preferably at least 780 wt organic solvent» and optionally contain

on at least one AT fluid; Preferably includes water. Subsequently; (JS) more preferably at least 798 wt; more preferably at least 9 wt. of current mainly from the organic solvent; preferably of acetonitrile” consisting of the organic solvent; preferably aceto nitrile; water; which is at least 5 760 by weight; preferably at least 770 wt.; more preferably at least 775 wt.; more preferably at least 780 wt. of stream from the organic solvent; Preferably acetonitrile. Said scavenging is carried out preferably at the temperature of said stream consisting principally of the organic solvent; preferably of acetonitrile” in the range from 20 to 90 °C; more preferably in the range of 25 to 80°C; 0 more preferably in the range from 30 to 70 degrees gia in an alternative preferred form; The present process further includes the preparation of the feed stream in (A1) by mixing a stream comprising propane; A stream containing hydrogen peroxide or a source of hydrogen peroxide; a stream comprising the organic solvent; Where step (b) includes (b1) stopping a stream containing hydrogen peroxide or a source of hydrogen peroxide; 5 (b2) Off Stream Incorporating Quand) and Stream Incorporating Organic Solvent; (b3) optionally depressurize and empty the reactor; where (B2) is performed preferably at least 30 minutes over (BY) more preferably at least 60 minutes; after shall (b1). step (c) 0 according to step (c); The catalyst is washed with a liquid aqueous system. It is understood that the possible constituents of the liquid aqueous system according to (c) and corresponding amounts of the foregoing on the gail described Led after are for the liquid aqueous system used in (c) prior to its addition to the catalyst comprising a titanium-containing zeolite. in general; A liquid water system according to (c) is not limited by the amount of water contained in it. 5 The liquid aqueous system may thus contain for example at least 750 wt., or at least 775 wt., or at least 785 wt. of water; Based on the total weight of the liquid aqueous system. on about

favorite; The liquid aqueous system according to (c) contains at least 795 wt. at (BY) most favourably at least 9 wt. more favourably at least 799.9 wt.

At least 9 by weight of sly water over the total weight of the liquid aqueous system. The water used in (c) may be obtained from any suitable source. preferably water

Used in (c) is demineralized water or condensate p600060401.

preferably The liquid aqueous system according to (c) contains methanol only in trace amounts; while preferably free or at least essentially free of methanol. preferably The liquid aqueous system according to (c) contains at most 75 wt more preferably 71 wt; more preferably 70.1 wt.; more specifically Semis 70.01 wt.; on about

0 more preferably 70.001 wt. More Sain 70.0001 wt. than methanol; al is the total weight of the liquid aqueous system. preferably The aqueous system Bll according to (c) contains hydrogen peroxide only in trace amounts; while preferably free or at least essentially free of methanol. preferably The liquid aqueous system Gy (c) contains at most 70.1 by weight; on about

5 favourited 70.01 wt.' more favourably 70.001 wt.; more preferably 70.0001 wt. of hydrogen peroxide; ly is the total weight of the liquid aqueous system. preferably The liquid aqueous system according to (c) has dad a pH ranging from 4 to 10; preferably from 7 to 9 as indicated by the electrode pH. specifically preferably; A liquid aqueous system according to (c) consists of water.

The washing in (c) may be carried out in any conceivable container thus the shal may be washed eg in the reactor containing the catalyst or in any other suitable vessel if the catalyst is removed from the reactor for washing in (c). preferably The shal washing in (c) takes place in the reactor containing the catalyst. Subsequently; The washing in (c) is carried out preferably in the Gaal-containing reactor where

5 The liquid aqueous system according to (c) contains at least 795 by weight; Preferably 799 wt

at least » more favorably 799.9 by weight at least » more favorably 799.99 by weight

by weight at least of water; ly is the total weight of the liquid aqueous system.

Washing in (c) can be performed in either a batch pattern or a continuous pattern. If washing is done in batch mode; Done

Contacting the catalyst one or more times with a specified amount of liquid aqueous system. Washing can be done thus

5. By immersing the catalyst in the liquid aqueous system. During flushing it is possible to subdue the water system

The liquid together with the catalyst to stir. It is possible when the washing in (c) is performed with a pattern

batch The liquid hydroponic system can be replaced one or more times.

If washing is carried out in a continuous pattern; The catalyst is continuously contacted with a stream of liquid aqueous system.

If the reactor containing the catalyst is placed vertically and the washing is performed in the reactor or the washing is performed outside the 0 reactor in any other suitable vessel (Buy) the washing can be performed either in an upward flow pattern or

in a downward flowing pattern; Preferably in a downward flowing pattern. Preferably » is made

Washing in (C) is in a continuous pattern. More specifically, the washing in (c) is performed in a continuous pattern in

The reactor containing the catalyst.

Subsequently; The washing in (c) is carried out preferably in a continuous pattern in the reactor containing the catalyst where the liquid aqueous system (gins) according to (c) is at least 795 by weight; preferably

At least 9 wt » most favourable at least 799.9 wt » most favour

at least 9 by weight of water; Bl is the total weight of the liquid aqueous system.

Preferably the shal is washed in a continuous pattern in a tube reactor or a tube reactor

With the help of the liquid water system having a liquid hourly space (LHSV) velocity of 0 in the range of 1 to 20 m/h; More preferably from 5 to

5 m/h; More preferably 5 to 10 m/hr. The velocity is determined by

The hour for the liquid in (c) as the flow rate of the liquid aqueous system in cubic centimeters per hour

Divided by the total cross-section in square meters of an empty reactor tube or tubes

of the reactor if a Gua ctube bundle reactor is used the tube has a constant diameter of 5 over its entire length and the tubes have constant diameters across its entire length respectively.

Subsequently; The washing shal in (c) is carried out preferably in a continuous pattern in a tubular Jolie or tube-block reactor containing Gina) where (ging the liquid aqueous system is at least 795 wt.; preferably at 799 wt. least; more preferably at least 799.9 wt; most preferably Shuai at least 799.99 wt of water; ly on Maa) the weight of the liquid aqueous system” and is conducted with the help of the liquid aqueous system having a vacuum velocity per hour of the liquid in a range of 1 to 20 m/h; more preferably 5 to 15 m/hr; More preferably 5 to 10 m/hr. The washing can be performed in (C) at any temperature suitable for the liquid aqueous system. preferably The washing is performed in (c) at a temperature of the liquid aqueous system in the range from 30 to 90 °C; Preferably from 40 to 80 degrees Celsius. The washing in (c) may be performed for any duration necessary to achieve sufficient washing of the catalyst used in (a2). preferably Lavage is performed in (C) for 1 to 25 hours; preferably from 1; 5 to 20 hours; more preferably from 2 to 12 hours; more preferably from 2:5 to 9 hours; More SMS from 3 to 6 hours. Jul 5 The washing in (c) shall be carried out preferably at a temperature of the liquid aqueous system in the range from 30 to 90°C s.d. 2.5 to 9 hours; Most preferably at a temperature of the liquid aqueous system in the range of 40 to 80 °C for 3 to 6 hours. Subsequently; The washing shal in (c) is carried out preferably in a continuous pattern in a tubular Jolie or tube-block reactor containing Gina) (ging the liquid aqueous system to at least 0 795 wt; preferably 799 wt. at least» more preferably at least 799.9 wt.; more preferably at least 799.99 wt. of water; based on the total weight of the liquid-aqueous system» and is performed with the help of the liquid-aqueous system having a vacuum velocity per hour of the liquid in the range of 5 to 15 m/hr at a liquid aqueous system temperature in the range of 30 to 0°C for 2.5 to 9 hours; more preferably 5 to 10 m/hr at 5 aqueous system temperature in the range of 40 to 80 °C for 3 to 6 hours Depending on the current process, washing in (C) is typically monitored by the total organic carbon concentration

in the liquid aqueous system after contact with the catalyst; The shal was washed in (c) preferably until the laa) limiting concentration of the organic creone was reached in the liquid aqueous system after contact with the catalyst. while the total organic carbon concentration reaches a maximum during washing in (c); A specific concentration preferably reached is referred to a value reached after the maximum limit has been reached. Preferably the washing in (c) is performed until the total organic carbon concentration of the liquid aqueous system after contact with the catalyst is 725 or less; Preferably 720 or Jil (preferably 5 or less; preferably 710 or less” more preferably Sain 75 or less; more preferably 74 or less” more preferably aan 73 or oi more preferably Tuas 72 or less” over 0 more preferably 71 or less than the maximum Man) of the concentration of the organic creon die detected during the wash in (c); where the total volume of the liquid aqueous system is equal to or greater than the internal volume of the reactor. It is understood that the total organic creone concentration is determined in accordance with German Industry Standards (EN) European number 1484. The time point when step (b) is performed and the feed stream input to reactor 5 is stopped to allow washing in (c) is chosen as follows: Preferred based on the lower selectivity Lad for the formation of propylene oxide in (21) relative to the average reaction selectivity in (A2) during the first 100 h of the step (a) procedure. It is understood that the selectivity for Lad is related to the formation of propylene oxide in (A2) ) in the context of the present process is the selectivity Lad for the formation of propylene oxide in (a2) based on hydrogen peroxide calculated as shown in comparative example 1. Hence; step (b) can be performed on example 0 when the selectivity for Lad has decreased for Formation of propylene oxide in (A2) by 715 or less; or by 710 or less; or by 76 or less by the mean reaction selectivity in (A2) during the first 100 hours of chal step (a). » Step (b) is performed when the selectivity Lad for propylene oxide formation in (21) has decreased by 74 or less; at n 73 or less favourable” more favourable, 72 or less for the mean reaction selectivity in (a2) during the first 5 100 hours of the step (a) procedure.

Phase (1) also includes repeating the sequence of steps (a) to (c) “times where” is an integer number and equal to at least 1. Thus » the sequence of steps (a) to (c) is repeated at least once before stage (2) is performed. Preferably; it is » in the range from 1 to 10 thus 1; 32 4 65 7 8 9 or 10. on More typically Saas is « in the range from 1 to 6 therefore 32 4 5; or 6. More specifically Sans is « in the range from 1 to 4 ull 1 2 3 , or 4. Depending on the operation the current; preferably only the catalyst obtained from (b) is washed with a single liquid aqueous system (sing at least 795 wt; more preferably at least 799 wt” more preferably at least 799.9 wt” at towards more Shas 799.99 with at least 0 wt. of water based on the total weight of the liquid aqueous system. This washing is preferably performed in a continuous pattern. Hence, it is preferable that the catalyst be treated with the same liquid system between step (b) and stage (2) what except the liquid aqueous system containing at least 795 wt; more preferably at least 799 wt; more preferably at least 799.9 wt” more preferably at least 799.99 wt of water based on the total weight of the aqueous system J questioner. 5 therefore; Preferably the dallas shal is not done before or after with a different liquid aqueous system; preferably with any different liquid system; where flushing of the reactor with organic solvent is not excluded; Preferably acetonitrile in (b) in this preferred form. according to the current process; The catalyst obtained from (b) is preferentially not treated with a gas stream consisting of; preferably including optionally ozone 0; (c) also includes drying the washed catalyst. if dried; Said drying preferably involves contacting the catalyst with a gas stream comprising nitrogen; preferably at the temperature of said gas stream in the range from 40 to 200°C; more preferably in the range of 55 to 150°C; more preferably in the range from 70 to 0° gia of the present invention; It is preferable that the aforementioned drying not be carried out after washing step (C) 5, after which calcination is not performed, i.e. it is carried out after washing step (C), after which stage (2) is performed.

Stage (2) The present process of regeneration also includes (2) stage comprising the calcination of the catalyst obtained from (c) after repeating the sequence of steps (a) to (c) several times.

preferably The calcination is performed in (2) at a catalyst bed temperature in the range from 0 to 600 °C; preferably 350 to 550°C; More preferably from 400 to 500° Age calcination may be carried out in (2) in a stationary ambient gaseous atmosphere or in a gas stream in contact with the catalyst. Preferably » calcination is performed in (2) in a gas stream. in general; The gas stream is not limited

0 mentioned on the components in it. preferably Said gas stream comprises oxygen, preferably oxygen and nitrogen. in general; The said gas stream comprising oxygen is not limited; preferably oxygen and nitrogen over the source used for oxygen; Preferably oxygen and nitrogen. preferably air; light air or a combination of the above; More preferably air or light air is used as the source. Subsequently; Calcination is performed in (2) on

5 preferably in a gas stream comprising oxygen; preferably oxygen and nitrogen” wherein the oxygen-comprising gas stream is; preferably oxygen and nitrogen, preferably air, light air, or a mixture of the above; More preferably air or light air. Thus calcination is carried out in (2) preferably at a temperature of the catalyst bed in the range from 300 to 600 °C; preferably 350 to 550°C;

0 more preferably from 400 to 500 °C in an oxygenated gas stream (Cag silly wherein the oxygenated gas stream; preferably oxygen and nitrogen) is preferably air; light air; or a mixture of the above, more preferably air or light air Calcination may be carried out in (2) for any period necessary to achieve sufficient calcination of the catalyst in the present process of regeneration

5 catalyst. Preferably » calcination is carried out in (2) for a period of 1 to 15 hours; preferably 2 to 10 hours; More preferably 3 to 7 hours.

July Calcination is carried out in (2) preferably at a catalyst bed temperature in the range from 300 to 600 °C s.a.d. 1 to 15 hours; more preferably 350 to 550°C for 2 to 10 hours; more preferably 400 to 500°C 3 to 7 hours in an oxygen-containing gas stream; preferably oxygen and nitrogen” wherein the oxygen-comprising gas stream is; preferably oxygen and nitrogen.” preferably air» light air; or a combination of the above; More preferably air or light air. Calcination can be performed in (2) in any possible container. Subsequently; Calcination may be carried out in (ii) for example in the reactor containing the catalyst or in any suitable AT vessel; In the case of removing the catalyst from the reactor for calcination in (2). preferably Calcination is performed in (2) in the 0-containing reactor over the catalyst. The sequence of stages (1) and (2) in the present process of catalyst regeneration can be repeated “times before catalyst disposal so that”: Ble is an integer equal to 1 over (JY) where in each iteration of the sequence of stages (1) and ( 2)) n is the same or different. Subsequently; The sequence of stages (1) and (2) is repeated at least once, so that in each iteration of the sequence of stages (1) and (2); similar or different. Preferably » 0 is in the 5 range from 1 to 10 and therefore 4 321; 5; 6; 7 8; 9 or 10. More specifically, Senin ““ is in the range from 1 to 6 hence 1 2 3; 4; 5; or 6. More generally m Sati is in the range from 1 to 4 and therefore 1 2; 3; or more preferably A” 0 is equal to [5 432; 6; 7 8; 9 or 10 Lin « equals 1; 32 4; 5». 6« 7 8 9 or 10) more favorably 1 – 2 3; 4 5; or 6 more preferably 0 2,1 3, or 4. Suns « equals 2d 3;4; 5; or 6 Lin « equals 1; 2; 33 5< 6 7 8 9 or 10 more preferably 1 2 3 4 5; or 6” more preferably 1 2 3; or 4. more preferably ; “ equals 1; 2 3; or Lind 8 equals 1; 2; 3 6 7 8 9 or 10 more preferably 1 – 2 3 4” 5; or 6” more preferably Suni 1 32 or 4. 5 regenerated catalyst

The present invention further relates to a regenerative catalyst comprising a zeolite containing titanium as the active material

A catalyst that can be or has been obtained by the process according to the present invention and in the manner

described above.

Preferably the regenerated catalyst according to the present invention in the propylene oxide preparation process exhibits a differential conversion temperature of at most 5 K; preferably 2 Kelvin at most; more on

Preferably 1 K at most Cus the differential conversion temperature is defined

conversion temperature as an absolute difference between

(17) The temperature at which a predetermined conversion of hydrogen peroxide is achieved in a preparation process

The aforementioned propylene oxide where the regenerated catalyst is used as a catalyst and

0 (b1) The temperature at which said predetermined conversion of hydrogen peroxide is achieved in said propylene oxide preparation Cus The corresponding new catalyst is used as a catalyst under other identical epoxidation reaction conditions. After a certain run time a decrease in the catalytic activity of the catalyst comprising titanium zeolites as Gia dads is observed in the epoxidation reaction. relates to low catalytic activity

5 a direct reduction in the conversion rate of at least one of the coal materials i.e. the olefin and/or epoxidation agent; The lower conversion rate can be compensated for by increasing the overall reaction temperature. This suggests that with continued use of the catalyst a gradual increase in the reaction temperature relative to the starting temperature is required; This makes the epoxidation process highly inefficient. however; By subjecting the catalyst comprising a zeolite containing spent titanium to a reaction

0 epoxidation to the regeneration process Gy of the present invention; Its initial catalytic activity can be restored. Initial catalytic activity here refers to the catalytic activity of a newly prepared catalyst. Where the catalytic activity is appropriately related directly to the reaction temperature under identical reaction conditions egal the efficiency of the spent catalyst can be deduced from the reaction temperature required to maintain the specified conversion rate. in the present case; The regenerated catalyst of all invention appears preferably in a preparation process

5 olefin oxide” degree ha conversion differs by at most 5 K; preferably 2 K on SY) more preferably 1 K at most than the conversion temperature of the new catalyst in

Other identical epoxidation conditions. It is also preferred that the catalyst regenerated according to the process of the present invention exhibit in the propylene oxide preparation process a “differential selectivity of at most 1” wherein the differential selectivity GUS is defined as absolute at 7 of the points between (a2) selectivity sly on hydrogen peroxide in the process Preparation of the aforementioned propylene oxide where the regenerated catalyst is used as a catalyst; and (ii) the selectivity sLY over hydrogen peroxide in said propylene oxide preparation process where the corresponding new catalyst is used as catalyst under other identical epoxidation reaction conditions; where the selectivity Bly over hydrogen peroxide is defined as moles of propylene oxide produced 0 divided by moles of hydrogen peroxide spent 100% (Sa) Determination of the quality of the catalyst comprising a zeolite containing regenerated titanium according to the process of the present invention also by comparing the selectivity of the regenerated catalyst The selectivity of the new catalyst under other identical epoxidation conditions After the use of Wal extender a decrease in the selectivity of the catalyst is typically observed. of at most 1 mole points from the selectivity of the new catalyst under other identical epoxidation reaction conditions.Continuous process for the preparation of propylene oxide of the present invention” The epoxidation reaction is preferably carried out in more than easily Jolie eg in at least two reactors; three reactors; or dal reactors, where reactors 0 are run in parallel. Depending on the design of this process, preferably during catalyst regeneration at a specified elie, the dependent reaction is performed Mix the epoxide in one or more of the remaining reactors. Subsequently; Propylene oxide can be prepared in a continuous way Ag at the same time » innovative regeneration can be carried out. It can be preferred that according to the design of the process; The epoxidation reaction is initiated in at least two reactors sequentially with an appropriate delay between the corresponding start times. 5 The present invention further relates to a continuous process for the preparation of propylene oxide comprising (1) a stage comprising

(a) Continuous preparation of propylene oxide in a first reactor comprising (a1) the introduction of a feed stream comprising Omg hydrogen peroxide or a source of hydrogen peroxide; the organic solvent in the first catalyst containing reactor comprising titanium zeolite as the catalyst active material; (ii) subjecting the feed stream according to (a1) in the first reactor to epoxidation conditions in the presence of the catalyst resulting in a reaction mixture comprising propylene oxide and the organic solvent; (31) Remove a product stream comprising propylene oxide and an organic solvent from the first reactor; (b) stop feeding the feed stream into the first reactor; (c) wash the catalyst with a liquid aqueous system; (Cz) SCT) ‘‘ times so that ‘’ is an integer number equal to at least 1; the propylene oxide preparation process also includes (12) stages including calcination of the catalyst obtained from (c”) after a succession of Steps () to (c) ‘‘ times, where the stages (11) to (72) GEA) are repeated m’ times such that !0 is an integer 5 equal to 1 over (JY) where In each repetition of the sequence of steps (C1) to (2”); ““ is the same or different; the propylene oxide preparation process also includes (1”) a stage comprising (7) a second Jolie continuous preparation of propylene oxide comprising 0 (1) Introduce the feed to dade containing propane; hydrogen peroxide or a source of hydrogen peroxide; and the organic solvent in the second catalyst-containing reactor comprising titanium-bearing zeolite as the catalyst; (2) subject the feed in accordance with (a1) in the second reactor to ambient conditions p epoxide treatment in the presence of the catalyst resulting in a reaction mixture comprising propylene oxide and the organic solvent; 5 (iii) remove a product stream comprising propylene oxide and the organic solvent from the second reactor; (b) Stop feeding the feed stream into the second reactor;

(c) washing the catalyst with a liquid aqueous system;

Stage (71) also includes repeating the sequence of steps (A”) to (C”) ““ times so that “0” is a phrase

for an integer number equal to at least 1; The process of preparing propylene oxide also includes:

(2) A stage comprising the calcination of the obtained (Tz) catalyst after repeating the sequence of steps

( ) to (2) ““ times;

Where the stages (1”) to (2) successively repeat 07 times with “0” being Ble for a digit

true and equal to at least 1; Where in each iteration of the sequence of steps (1”) to (2”); “or” is the same

Differs from;

where during at least one sequence of steps (b”) and (c”) or at least one sequence of steps (b”); 0 (c) and (2); Propylene oxide is prepared according to (1)

The present invention is further characterized by the following embodiments and combinations according to embodiments specified by dependencies

Debate:

1. Process for catalyst regeneration comprising a zeolite (ging) titanium as the catalytic active material; comprising

(1) 5 stage comprising ( ) continuous preparation of propylene oxide comprising

(a1) feed stream input comprising two motors; hydrogen peroxide or source of hydrogen peroxide;

and organic solvent in a catalyst containing reactor comprising titanium-containing zeolite

as an active substance tha

(ii) subjecting the feed stream according to (a1) in the reactor to epoxidation conditions in the presence of taal 0 resulting in a reaction mixture comprising propylene oxide and the organic solvent;

(a3) remove a product stream comprising propylene oxide and the organic solvent from the reactor;

(b) stop feeding the feed stream into the reactor;

(c) washing the catalyst with a liquid aqueous system;

Stage (1) also includes repeating the sequence of steps (a) to (c) “times where” is 5 whole numbers equal to at least 1; The renewal process also includes

(ii) a stage comprising the calcination of the catalyst obtained from (c) after the sequence of steps (a) to (c) was repeated several times; where optionally iterating the sequence of stages (1) to (2) hem where ““ is an integer and equal to 1 over (JR) where in each iteration of the sequence of stages (1) to (2); similar or different.

2. Process according to Model 1; Comprising preparation of the feed stream according to (A1) by mixing a stream comprising propane; A stream containing hydrogen peroxide or a source of hydrogen peroxide; and a stream containing the organic solvent. 3. Process according to Model 2 where the feed stream according to (A1) also includes at least one salt that includes potassium.

0 4. Process according to Model 2 where at least one salt comprising potassium is one or more of potassium dihydrogen phosphate cdipotassium hydrogen phosphate and potassium formate .formate 5. Operation according to Model 3 or 4; The preparation of the feed stream according to (1) includes the incorporation of a water stream

5 comprising at least one dissolved salt comprising potassium with a stream comprising propene; or with a stream comprising hydrogen peroxide or a source of hydrogen peroxide; or with a stream comprising an organic solvent; or with a mixed stream of two or three of these streams; preferably with a stream comprising hydrogen peroxide or a source of hydrogen peroxide; or with a stream comprising an organic solvent; Or with a mixed stream of the above.

0 6. Operation according to any of the models 1 to 5; where the organic solvent is methanol or acetonitrile, preferably acetonitrile.

7 process according to any of forms 1 to 6; where the molar ratio of propene to hydrogen peroxide or to hydrogen peroxide produced from the hydrogen peroxide source in the feed according to (a) is in the range from 1:1 to 1.6:1; Preferably from 1.1:1 to 1.55:

5 1 more favorably from 1.2:1 to 1.5:1; Most preferably from 1.30:1 to

. :.5

8. The process according to any of embodiments 1 to 7 where the reactor according to (a2) is Jolie operated under

isothermal.

9. The operation according to any of Forms 1 to 8 where according to (A2); The temperature of the reaction mixture is controlled

isothermally using heat Jil medium; Preferably pass through the transfer medium

Heat through a reactor cap.

0. The process is according to Model 9, where the epoxide curing conditions according to (A2) include temperature

Epoxidation reaction in the range from 20 to 100 °C; Preferably from 25

to 80 °C; more preferably from 30 to 60°C; where the degree is defined

Heat of the epoxide treatment reaction as the degree of Hla heat transfer medium prior to controlling the temperature of the 0 reaction mixture » preferably as the temperature of the heat reducing medium at the inlet of the reactor jacket operating in

isothermal conditions.

1. Process according to any of Forms 1 to 10 (where the epoxide curing conditions in (A2) include

Epoxidation reaction pressure in the range from 5 to 100 GL preferably from 10

to 32 JL more preferably from 15 to 25 JL where the pressure of the epoxided Jolin 5 is defined as the pressure at the outlet of the reactor operating under isothermal conditions.

2. the operation according to any of Forms 1 to 11; Where titanium-containing zeolite has a structure

Frameset (MFT) Frameset MEL Frameset 01177177 Frameset Type 211717 Frameset or Mixed Structure

of two or more of these framework structures” preferably MFI framework architecture

7 or more framework type 1017177 Sawai frame structure MWW or frame structure 0 type MWW

3. Process according to any of Forms 1 to 12; Where 799 is made by weight on “JBI” preferably

5 by weight at least»; More preferably at least 799.9 wt. of frame construction

for titanium-containing zeolites from silicon, titanium»; and oxygen.

4. Process according to any of embodiments 1 to 13 wherein the titanium-containing zeolite includes 5 one or more aluminium; boron; zirconium; valium; niobium; tantalium, chromium;

molybdenum; tungsten; manganese; Iron; cobalt; nickel; zinc; gallium; germanium; indium;

tin; alia palladium; platinum; gold; cadmium; preferably one or more boron; zirconium; Valium; niobium; tantalium»; chromium; molybdenum; tungsten; manganese » iron; cobalt; nickel; zinc; gallium; germanium; indium; tin; lead, palladium; platinum » gold; cadmium; More preferably zinc.

15. The operation according to Form 14; Whereas, the titanium-containing zeolite included in the catalyst according to (A2) has a MWW framework structure that includes zinc; They include titanium” is considered elemental titanium; in an amount in the range from 0.1 to 75 wt.; preferably from 1 to 72 wt.; based on the total weight of the titanium-containing zeolite” and includes ll calculated as elemental zinc; in an amount in the range from 0.1 to 75 wt.; preferably from 1 to 722 wt.; based on total

0 weight of titanium-containing zeolite. 6. Process according to any of Forms 1 to 15; Whereas, the catalyst comprising titanium-containing zeolite is present in the reactor as a fixed bed catalyst. 7. Process according to any of embodiments 1 to 16) where dag the catalyst comprising titanium-containing zeolite in the reactor as a template comprising titanium-containing zeolite; where template 5 preferably comprises titanium-containing zeolite in an amount of 70 to 780 wt. and binder in quantity in the range of 30 to 720 wt.; based on total mold weight; (Cus the binder is preferably a silica binder 8. Process according to any of embodiments 1 to 17) Comprising the preparation of the feed stream in accordance with (a1) by mixing a stream comprising the browine; a stream comprising hydrogen peroxide or a 0 hydrogen peroxide source; and a stream comprising the organic solvent; Cus to stop the introduction of the feed stream into the reactor according to (b); preparing comprising Feed stream in accordance with (A1) to (117) stop the dads stream on the hydrogen peroxide or hydrogen peroxide source and keep mixing the propane-containing stream and the organic solvent-containing stream to obtain the feed stream; (12) stop the propane-containing stream and the propane-containing stream organic solvent; 5 where (110) is performed on n preferably at least 30 minutes» more preferably at least 60 minutes; AFTER (121) and WHERE; AFTER (A12) the reactor is optionally depressurized and evacuated.

9. Process according to any of Forms 1 to 18; wherein the liquid aqueous system according to (C) contains “BY preferably at least 799 wt” more preferably 799.9 wt over (J) more preferably at least 799.99 wt of water; Based on the total weight of the liquid aqueous system. 20. Process according to any of embodiments 1 to 19 (where the liquid aqueous system according to (c) contains at most 75 wt; at most favourably 70.001 wt over SY most favourably 70.0001 wt most of methanol; Based on the total weight of the liquid aqueous system. 0 21. Process according to any of embodiments 1 to 20 wherein the liquid aqueous system according to (c) contains at most 1 by weight;. Preferably 70.01 wt max. more preferably 1 wt at most more preferably 70.0001 wt at most hydrogen peroxide; Based on the total weight of the liquid aqueous system. 2. The operation according to any of Forms 1 to 21 where according to (c); The catalyst is washed into reactor 5 containing the catalyst. 3. The operation according to any of Forms 1 to 22; Where the total volume of the liquid aqueous system used in accordance with (c) is equal to or greater than the internal volume of the reactor. 4. The process according to any of the models 1 to 23 where the washing is carried out according to (c) in a continuous pattern. 5. The operation according to Form 24; where the reactor according to (a) is a tubular reactor or a 0-tube reactor and the washing according to (c) is performed with the aid of the liquid hydroponic system at a vacuum velocity per hour of the liquid in the range of 1 to 20 m/hr; preferably 5 to 15 m/hr; More Sass 5 to 10 m/h. 6. The process according to any of embodiments 1 to 25 wherein the washing is carried out according to (c) at a temperature of the liquid aqueous system in the range from 30 to 90 °C; Preferably from 40 to 5 80 degrees Age

7. Process according to any of the models 1 to 26 where the washing is carried out according to (c) for a period of 1 to 25

hour; preferably sad 1.5 to 20 hours; More preferably sad 2 to 12 dele

more preferably sad 2.5 to 9 hours; Most preferably for 3 to 6 hours.

8. Process according to any of embodiments 1 to 27 whereby washing is performed according to (c) until the total organic carbon concentration of the liquid aqueous system after contact with the catalyst is 725 on IYI as

Preferably 720 on ASV Preferably 715 at most; preferably 710 at most;

more preferably 75 at most; More preferably 71 at most than the maximum total

For the concentration of the organic creon die detected during the wash in (c).

9. The process is according to any of Models 1 to 28 where the sequence of steps (b) and (c) is performed when

0 The selectivity of the epoxide treatment according to (A2) decreased by 74; preferably by 73; more favourably by 72 relative to the average Jolin selectivity epoxided under (a2) during the first 100 hours of the step procedure of) where the selectivity of the epoxidation reaction is defined as the molar amount of propylene oxide obtained in (a2) with respect to the molar amount of hydrogen peroxide converted in (A2).

5 30. The operation is according to any of the models 1 to 29 where « is in the range from 1 to 10; preferably from 1 to 6; Most preferably from 1 to A

1. Process according to any of embodiments 1 to 30 in which the calcination is carried out according to stage (2) at a catalyst temperature in the range from 300 to 600°C; preferably from 350 to 550°C; more preferably from 400 to 500 degrees Celsius.

0 322. Process according to any of embodiments 1 to 31 where the calcination is carried out according to stage (2) using a gas stream comprising oxygen; preferably oxygen Congually where the gas stream is preferably air; light air or a combination of the above; more preferably air or air 3. Operation according to any of Models 1 to 32; Where calcination is carried out according to stage (2) for a period of 1 to

5 15 hours; preferably 2 to 10 hours; More preferably 3 to 7 hours.

4. The process is according to any of models 1 to 33, where the calcination is carried out according to stage (2) in the reactor

which contains the catalyst.

5. The process is according to any of models 1 to 34 where the sequence of stages (1) to (2) Clem is repeated

where « is an integer in the range from 1 to 10; preferably from 1 to 6; on

Towards more favorable from 1 to 4.

6. Regenerative catalyst comprising a zeolite containing titanium as the catalytic active material; can get

obtained or obtained through the process under any of Forms 1 to 35.

7. The regenerative catalyst according to Model 36) where the titanium-containing zeolite has a framework structure

(MWW where at least 799 wt” preferably at least 799.5 wt; about 0 more Sami at least 799.9 wt” framework structure of titanium-containing zeolite consists

of silicon; Titanium and oxygen, as the titanium-containing zeolite includes approximately

preferred over zinc; Whereas, the titanium-containing zeolite includes titanium, calculated as titanium

racist in an amount in the range from 0.1 to 75 wt.; preferably from 1 to 722 wt.;

Bly on the total weight of the titanium-containing zeolite” and preferably zinc-containing; 5 Calculated as elemental zine in an amount in the range from 0.1 to 75 by weight; on about

preferred from 1 to 72 by weight; Based on the total weight of the titanium containing zeolite.

8. Regenerated catalyst according to pattern 36 or 37; Wherein the regenerated catalyst is a zeolite-incorporating block

contains titanium” as the mold preferably includes titanium-containing zeolites

in an amount in the range from 70 to 780 wt. and the binder in an amount in the range from 30 to 720 0 wt.; Based on Gross Mold Weight» where the binder is preferably a binder

of silica.

9. Regenerated catalyst according to any of Models 36 to 38; who appears; in the oxide preparation process

propylene” differential conversion temperature of 5 Kelvin at most; Preferably 2 Kelvin on

“SY most preferably 1 K at most” where the differential conversion temperature 5 is defined as the absolute difference between

(17) The temperature at which a predetermined conversion of hydrogen peroxide is achieved in a preparation process

Said propylene oxide where the regenerated catalyst is used as catalyst and (b1) the temperature at which said previously determined conversion of hydrogen peroxide is achieved in said propylene oxide preparation Cus the corresponding new catalyst is used as catalyst under other identical epoxidation reaction conditions.

40. The regenerated catalyst according to any of Models 36 to 39; who appears; in the propylene oxide preparation process “a differential selectivity of at most 1” where the differential selectivity is defined as an absolute difference of 7 points between (20) the selectivity aly on hydrogen peroxide in the said propylene oxide preparation process where the regenerated catalyst is used as a catalyst; and

0 (b2) selectivity sly over hydrogen peroxide in said propylene oxide preparation process where the corresponding new catalyst is used as catalyst under other identical epoxidation reaction conditions; Where the Bly selectivity to hydrogen peroxide is defined as moles of propylene oxide produced divided by moles of hydrogen peroxide consumed x 100.

1. A continuous process for the preparation of propylene oxide, including:

5 (1) A stage comprising (a) continuous preparation of propylene oxide in a first reactor comprising (a1) introducing a feed comprising Omg hydrogen peroxide or hydrogen peroxide source; and organic solvent into the first reactor containing the catalyst comprising titanium-containing zeolite as catalyst active material;

0 (ii) subject the feed stream according to (A1) in the first reactor to epoxidation conditions in the presence of the catalyst resulting in a reaction mixture comprising propylene oxide and the organic solvent; (a3) Remove a product stream comprising propylene oxide and the organic solvent from the first reactor; (b) stop feeding the feed stream to the first reactor; (c') Washing of the catalyst with a liquid aqueous system;

5 stage (1”) further includes repeating the step sequence (Cz) (CT) ‘‘ times such that ‘’ is an integer number equal to at least 1; The process of preparing propylene oxide also includes:

(72) a stage that includes calcination of the catalyst obtained from (Tz) after repeating the sequence of steps

) to (2) '« times;

Where optionally the sequence of phases (11) is repeated to (2) Chem so that !00 is a number

true and equal to 1 on (JB) where in each iteration of the sequence of steps (1”) to (2); corresponds to ©« or

Differs from;

The propylene oxide preparation process also includes:

(1") stage includes

(7) Continuous preparation of propylene oxide in a second Jolie comprising

(a1) the introduction of a propane comprising feed; hydrogen peroxide or source of hydrogen peroxide; 0 and the organic solvent in the second reactor containing the catalyst containing zeolite

on titanium as a catalytic active material;

(12) subjecting the feed stream according to (A1) in the second reactor to epoxide treatment conditions in the presence of

the catalyst resulting in a reaction mixture comprising propylene oxide and the organic solvent;

(iii) remove a product stream comprising propylene oxide and the organic solvent from the second reactor; 5 (b) stop feeding the feed stream to the second reactor;

(c) Washing of the catalyst with a liquid aqueous system;

Stage (71) also includes repeating the sequence of steps (A”) to (C”) ““ times so that “0” is a phrase

for an integer number equal to at least 1; The process of preparing propylene oxide also includes:

(2) A stage comprising the calcination of the catalyst obtained from (Tz) after repeating the sequence of steps 0 () to (c) “then”

where optionally the sequence of phases (C1) is repeated to (2) ahem” so that “0 is Ble for a number

true and equal to at least 1; Where in each iteration of the sequence of steps (1”) to (2”); “or” is the same

Differs from;

where during at least one sequence of steps (b”) and (c”) or at least one sequence of steps (b”); 5 (c) and (2); Propylene oxide is prepared according to (a).

The present invention is further illustrated by the following figures; reference examples; examples; and comparative examples. Brief Explanation of the Drawings Figure 1 shows the schematic diagram of the process according to Reference Example 2. In Figure 1 the letters and numbers have the following meanings: a “I” epoxidation unit b epoxidation unit c distillation unit d unit Distillation 0 e part stream distillation unit g mixer-settler unit h acetonitrile recovery unit Js yi i Sang recycling acetonitrile 5 (1) (20) Streams according to a preferred process on dng in particular as described in the examples “S02” “S01” SO to ¢S2 ¢S4 TAQI L2 to BL2 ¢TL2 ¢TL2 ¢TL1 currents According to a preferred process as described by the general description and examples Fig. 2 shows a schematic diagram of a partial current distillation Uy of the unit presented in Fig. 1 in detail. In Fig. 2 the letters and numbers have the following meanings: 0© 1st fractionator in micro-stream distillation unit “and” 2nd fractional unit in micro-stream distillation “and” (13) (113)» (14) (15) (115)« ( 5ab) “(z15) (16)” (19); (20) Currents according to a particularly preferred process as described in the examples Lee 2 ¢S4 “S3 DAKE FLAT S4c ch 112 5 Currents according A preferred process as described by the general description and examples.Detailed description 1:

Reference Example 1: Preparation of a mold containing MWW structure spray powder containing

titanium and zinc

The catalyst was prepared as a template as described in International Application No. 117536/2013

A2; in Example 5; Specifically in Examples 6-5-1-5; pp. 99-83. Methods that characterize the said template (ad) in cited examples 6-5-1-5 are described in referenced examples 10-2.

On pp. 66-71 of International Application No. 117536/2013a2. Distinctive characteristics are explained

of the catalyst in Figures 20-27 of International Application No. 117536/2013 A2 and the corresponding description of the figures

Mentioned on page 104 of International Application No. 117536/2013 A2.

Reference Example 2: Setting up an epoxidation reaction

0 for shortcuts; The diagrams are indicated by Figures 1 and 2; Generally described in

Shape Description section. All pressure values specified are absolute pressure values.

1-1 Preparation of the SO stream (step (a))

1 Epoxidation main reactor epoxidation main reactor (epoxidation unit 1)

5 The main reactor “A” is a Jolie with a vertically installed array of tubes comprising 5 tubes (length of tubes: 12 m, inner diameter of tube: 38 mm); Each tube is provided with a pivot-positioned multi-point thermocouple comprising 10 evenly spaced measuring points encased in a suitable 18 mm diameter thermocouple. Each tube was shipped with 17.5 kg of catalyst briquettes with MWW structure containing titanium and zinc as prepared according to the example

0 Reference 1 (Mouldings 0050180160). All remaining space at the end was ede with steatite spheres (3 mm in diameter). The heat of reaction was removed by circulating a hot-fixed Ji medium (water/glycol mixture) on the cap side in a co-stream to the feed. The flow rate of the heat transfer medium is set so that the temperature difference between the inlet and outlet does not exceed 1°C. The reaction temperature indicated below was determined as the temperature of the heat-reducing medium

5 The reactor shell is inserted at the outlet of the reactor; The pressure was controlled by a pressure regulator and kept Gb at 20 bar.

The reactor was fed from below with a single-phase liquid stream (1). The current (1) was prepared through

Mix four ks (2)» (3)» (3) and (4). The temperature of the stream (1) is not effectively controlled; however

It was usually in the range of 20 to 40 °C:

Stream (2) has a flow rate of 85 kg/hr. It consisted of at least 799.5 by weight of stream (2) from

Acetonitrile, propane and water. This stream (2) came from the lower outputs of the distillation unit by circulating aceto

(1) acetonitrile recycle distillation unit

- Stream (3) which has a flow rate of 15 kg/hr was the aqueous hydrogen peroxide solution in it

Hydrogen Peroxide Concentrate of 740 by weight ("raw/washed" Solvay grade by total content

Organic carbon in the range of 100 to 400 mg/kg. Aqueous hydrogen peroxide solution 00 was supplied from a storage tank; allowing for continuous feeding; And feeding it using a metering pump

suitable.

- The stream (13) was a water stream containing dissolved potassium formate.

another stream from the storage tank allowing continuous feeding; It was fed using

suitable metering pump. The potassium formate concentration was 72.5 wt.; The feed rate from stream (53a) 5 was 370 g/h. The stream (13) was thoroughly mixed with the stream (3) before the combined stream was mixed with the stream

resulting from the mixing of the two currents (2) and (4).

- Stream (4) was a dallas stream of pure acetonitrile (chemical order; of dneos purity of about

799.9 contains between 70-180 ppm by weight of Probio-nitrile » 5-20 ppm

million by weight of acetamide and less than 100 ppm by weight of water as an impurity). 0 "Sufficient new acetonitrile has been added to compensate for losses in the process. Under regular conditions; done

Add an average of 100 to 150 g/hr of treated acetonitrile.

The output stream (5) samples were collected from the epoxide-treated sang each

0 minutes to determine the concentration of hydrogen peroxide using the titanyl sulfate method

And to calculate the hydrogen peroxide conversion. The hydrogen peroxide conversion is determined to be 100 x (1- (Mow/min 5) where min is the molar flow rate of hydrogen peroxide in the reactor feed Mou s is

The molar flow rate of hydrogen peroxide at the reactor outlet. Based on peroxide conversion values

hydrogen obtained in the order »days The heat transfer medium input temperature was set to keep the hydrogen peroxide conversion essentially constant in the range of 90 to 92 7. The heat transfer medium input temperature was set at 30 °C at the start of the specified cycle with a fresh batch of epoxidation catalyst and topping up if necessary; To keep the conversion of hydrogen peroxide in the stated range. The required sale temperature increase was less than 1 [OAS] day.

The output stream (5) from the epoxided sang A was passed through a heat exchanging unit. The stream from the heat exchange unit (stream (6); 50) was fed to the epoxide unit ' B".

b) Epoxide dallas in the Finishing Reactor (Epoxide Treatment Unit B)

0 Termination Reactor B was a fixed bed reactor operated in an adiabatic manner. in this context; 'Ball suppressed' refers to a By mode of operation in which no active cooling is performed and under which the termination reactor is suitably insulated to limit heat loss.) Termination reactor B has a length of 4m and a diameter of 100mm. The reactor was filled with 9 kg of the same epoxidation catalyst that was used in the Jolie epoxide master A". The extra space was filled with a volume of balls

5 steatites (3 millimeters in diameter). Termination B reactor operating pressure was 10 bar which was kept constant by an appropriate pressure regulator at the reactor outlet. Termination Reactor B output samples were collected every 20 min to determine hydrogen peroxide concentration using the titanyl sulfate method. The effluent from the B-stream (6) termination reactor was depressurized into a flashing cylinder; both liquids and gases from this cylinder were fed to a separation shaft with a boiler separation boiler

column 20 light (distillation unit “C”). Stream (6) (SO stream) has an average acetonitrile content of 69 to 770 by weight; a propylene oxide content of 711-9 by weight as 79.8 by weight; a water content of 717 by weight; propene content of approximately 73 (ell) broyan content of approximately 70.05 by weight; hydrogen peroxide content of approximately 0 ppm by weight; glycolpropene content of approximately 70.1 by weight and oxygen content of approximately

5 about 150 eda per million by weight.

2-1 Separation of propylene oxide from stream 50 to obtain stream 51 (step (b))

a) Separation of light boiling products from stream (6) (stream (SO) to obtain stream (8) (stream 501) The stream (6) is sent to a separation column with light boiling (distillation unit (Tg) operated at 1 bar Distillation column is provided with length 8.5 meters diameter 170 mm 40 bubble trays evaporator at the bottom and condenser 5 at the top The column is operated as a tower [ Jue mixed washing/distillation tower Distillation As a washing agent, part of the bottom-product stream was extracted from distillation unit “D” (stream 11 about 300 kg/hr) cooled to 10 °C and introduced at the top of the column. The liquid and gaseous input streams entered the column at different points. The feed point gal) of the liquid from the stream (6) was above the bubble tray 37; the gaseous part of the stream (6) was introduced into the column above the bubble tray 8 0 (counted from above) The gaseous stream (7) exiting from the cooling medium included cooling means at the top of the column mainly broyans (included as impurities in the propane-pol pass rank user); Oxygen formed as a by-product and small amounts of light boilings (GAY) (acetonitrile (2-1 7 vol); propionaldehyde (about 200 vol-ppm); acetone sa) 100 volume-ppm; Ha (about 400 vol-ppm); carbon dioxide (CO) dioxide (about 400 vol-ppm) and acetaldehyde ula (about 100 vol-ppm) ); It was essentially free of propylene oxide (less than 300 vol-ppm). This overflow was sent to the glow to get rid of it. The lower stream from the light-boiling separation column (stream (8) i.e. stream (“SOT” has a temperature of 70 °C; a protein content of 100 to 200 ppm 0 by weight. b) Separation of propylene oxide from the stream (8) (Stream S01 to obtain stream 802) Stream 1 obtained in accordance with section 1-2a) above is introduced into a distillation column (distillation unit D) to separate the propylene oxide from stream 501. The column has a height of 50m and a diameter of 220mm and is supplied with (Sulzer BX64) packing with a total packing length of 27.5 jie 5 divided into 8 layers of 3060mm each and 2 layers of 1530mm each. Instantaneous flow distributors installed Column powered on

At an upper pressure of 750 mbar. Stream feed point 501 is located below the fourth filler layer; calculated from above. The overhead stream from the shaft was condensed and returned Us to the shaft as reflux (return ratio approximately 5:1). The rest has been taken (current (9)); which has a flow rate of 10.1 kg/h; As an by-product and as a base product consisting of propylene oxide, it has a purity greater than 799.9 by weight. The bottom-product evaporator was operated so that the concentration of propylene oxide in the bottom-product stream was less than 100 ppm wt. The temperature of the resulting downstream stream was about 69 °C. The 502nd was then divided into two parts. The larger gall of it (stream (10); flow rate about 85 kg/h) was sent to the next distillation column (distillation unit (“a” the remainder cooled (stream (11); 0-30 kg/hr) and recycled to the top of the light-boiling 0 separation column (distillate “C”) as a wash agent as described above in Section 2.1a).This 502 stream has an acetonitrile content of approximately 780 wt.; propylene oxide content Less than 100 ppm by weight Water content of about 720 by weight Propene glycol content of about 70.1 by weight and hydroxypropanol content of about 70.1 by weight c) Separation of low boiling point compounds from the stream (10) (Stream 502) To obtain the stream (S1 wd) (5) (13) The stream 502 obtained in accordance with section 1-2 b) above is introduced into the light-product separation column (distillation unit “e”). This has a height of 8 meters and a default diameter of 150 millimeters and is provided with 35 bubble trays The shaft is operated at an upper pressure of 2 bar and the current 502 is inserted above bubble tray No. 7 (m a number from the lower gall). The obtained 0 overhead stream (current (12); at a flow rate of about 1 kg/h) left the column at a temperature of 40 to 45 °C and was not condensed while the column was operated with no internal return current. besides acetonitrile (6500 ppm by volume); This overhead stream consisted mainly of nitrogen (which was used to maintain the shaft operating pressure at a value of 2 bar) and small amounts of light boiling products (acetaldehyde (900 ppm vol); oxygen 5 (300 ppm vol); and propion aldehyde. propionaldehyde (320 ppm by volume). This overflow was sent to the glow to get rid of it. The collection tank evaporator has been operated

By feeding it a constant amount (5 kg/h) of saturated steam at a pressure of 16 bar. The bottom part of the column was heated to 100 °C. The bottom output stream is formed; The ST is mainly coldly acetonitrile with the remainder being upper boiling products. This stream 51 has an acetonitrile content of about 780 by weight and a water content of about 720 by weight. 3.1 Division of Stream 51 into Streams 52 and 53 (Step (c)) Step (c); Stream split “ST” has a flow rate of 86 kg/h; obtained pursuant to Section 2.1 c) above; into two streams » streams 52 (stream 113 according to Fig. 1) and 53 (stream 14 according to Fig. 1). Stream 52 has a flow rate of 84 kg/hr and stream 53 has a flow rate of 2 kg/hr. The stream was subdued 53 »; 72.3 from the current 51; To the part stream distillation unit “and” (0 columns 9.5 m high, 85 mm in diameter and supplied with a length of 6.5 m of Rombopak OM metal structured wadding mounted in three identical layers. On top of the first layer of structured wadding felt from the top; ) in the first distillation column. The stream temperature was 53 60 + 3 °C. The first distillation column was operated at an upper pressure of about 1.4 bar and the bottom product temperature was 92 + 5 °C. No reflux was used. The amount of vapor was controlled which was fed to the bottom-product evaporator of the first fractionator such that the concentration of acetonitrile in the bottom-products was in the range from 10 to 725 wt.. Bottom-product stream 540 (stream 0 (15b); about 723 from stream 53) was removed. The stream was mainly from water (72-785 wt) and acetonitrile (10-724 wt). All analyzed high boiling point components (27 components) were in the range of 710-2 wt. upstream Steam portions stream 548 (stream 5) is not condensed.” which has a temperature of 85 + 3 degrees cgi and is passed to the bottom of the second hashing unit; i.e., the second distillation column” 12. Sda entered F2 below the last layer of the structured packing 5, felt from the top, 0.22, has a height of 9.5 meters, aly diameter of 85 millimeters, and was sng with a length of 6.5m of Rombopak OM metal structured 3-ply foam

identical. The second distillation column was run at an upper pressure of about 1.25 bar and the temperature was reached

Bottom Outputs 85 + 5 Degree Augie Top Stream Intensified; Steam parts stream Sde (current

(15c); 71 at most of the current 540); Completely by means of external condensation of the upper products

(not shown in Fig. 2) and used primarily by GIS to use the CES liquid stream as return to the second distillation column. The liquid bottom stream 54 (stream 15) was removed; it was passed to step

following (current recycling 54). Stream 54 has an acetonitrile content of approximately 780 by weight and content

Water is about 720 by weight.

sale) 5-1 Cycle Current 54 (Step (4))

a) Preparation of the liquid stream 55

0 stream 54 is mixed; (current 15 according to Fig. 1 and Fig. 2) with current 52 (current (113) according to Fig. 1 and Fig. 2). Subsequently; Stream 54 was piped back to the gid acetonitrile solvent stream block processor. The mixing took place at a point after where the stream 53 branched off from the stream 51. This combined stream having a flow rate of 86 kg/hr was mixed with the liquid stream © (indicated as stream (20) in Fig. 1 and Fig. 2) to give stream 85. It was The © stream is a new Gg yp stream

5 contains broyan (polymeric grade; purity > 796 wt; liquefied under pressure; feed rate: 10.9 kg/hr). for the current 55; The combined stream of 52 and 54 is also mixed with two other streams: lal the first of these streams is current (16) of Fig. 1; The said current is obtained from the upper part of the distillation unit “H”. The second of these currents is the current (19) according to Figure 1; The aforementioned current is obtained from the acetonitrile extraction unit “I”. Both streams are described

0 (16) 5 (19) in detail below.

b) Set the temperature of the stream 55 and separate the liquid phases L1 and 12

The stream 55 having a flow rate of 130 kg/hr + 10 kg/hr was then fed to a mixing-fixing unit operated at 18 bar and a temperature in the range of 15 + 5°C. The mounting tank has a volume of 5.3 liters. Two liquid phases 1.1 5 (L2) aqueous phase were obtained

5 2] and the organic phase 1.1. The upper organic phase 1.1 was removed from the settler tank as the current (17); The lower aqueous phase 12 was removed from the stabilization tank as the current (18).

Stream (17) which has a flow rate in the range of 110 kg/hr + 11 kg/hr. The stream (17) was then passed to a “la” acetonitrile recycle unit The stream (18) was passed to an hourly acetonitrile recovery unit from which the above stream (16) was obtained. The stream (17) thus obtained has an acetonitrile content of about 751-45 wt.; propene content of about 49-755 wt. and an ole content of about 2 to 75 wt. The stream (18) thus obtained has an acetonitrile content of about 721-19 “sll, a water content of about 79-781 by weight and a propane content of less than 70.5 by weight. c) Acetonitrile recovery (acetonitrile “H” extraction unit) to recycle as much solvent as possible; and to reduce the loss of acetonitrile; The current (18) was introduced to 0 distillation column from which the current (16) was obtained; also referred to as stream 712” as an overhead stream which in turn [sale] is recycled to the solvent stream as described above. for this purpose; A distillation column with a height of 9.5 jie and a diameter of 100 mm was used; Supplied with 50 bubble trays. The column is operated at an upper pressure of 1.5 bar with a return ratio of 1:4. The current (18) was fed to the column above the bubble tray 26 (counted from the lower sad). The temperature of the lower 5 outgrowths was about 113 degrees Celsius; The down-product consists mainly of water containing high-boiling-point by-products. The typical composition of the downstream stream was as follows (7 by weight indicated in parentheses): water (>99.0(¢) propylene glycol (0.5); acetonitrile (maximum 0.001); di(plug yn) dipropylene glycol (0.06) acetamide 0 (0.01) acetamide (0.03) total organic chiron content (2.4) After optional measurement and analysis, this 0 current was eliminated. The overproduct product had (current (16) = current ( TL2 ranges for typical composition (7 by weight indicated in parentheses): acetonitrile (80-75(¢) water (15-20));low-boiling products (eg proline; 1).As described above the stream is recycled (16) To the feed stream passed to the mixer-settler unit .d) Recycle acetonitrile (sale unit) Recycle acetonitrile “i”) Recycle acetonitrile” stream is introduced (17 ) obtained from the mixing-fixing unit “g” to a distillation column having a height of 10 m and a default diameter of 200 mm; equipped with 40

bubble tray. The column is operated at an overhead pressure of 18 bar with a reflux ratio of 1:4. The current (17) was fed to the column above the bubble tray 26 (filled from above). The upper product has been returned (current (19)); Also referred to as TLL stream containing mainly propane (about 7 vol.) with small amounts of broyan (about 1-73 vol.) is fed into a mixing-stabilizer “g” as described above. Subsequently; Excess propane has been removed from the steam (17) and recycled. The bottom product stream (stream (2); Wiad referred to as the stream (BLT) has a temperature in the range of 106 to 110 °C. The micro-operating variable is set Jie the energy input into the collection tank so that the amount of propane returned to the reactor with the stream (2) is in such a range that the molar ratio of propane to hydrogen peroxide in the stream (1) is about 1:1.43.0 to obtain the aforementioned feed rate of 15 kg/h for aqueous hydrogen peroxide, this means that the conditions need to be adjusted so that the broin flow rate in stream (2) is about 9.7 kg/h.Before the stream (2) is fed into the main epoxidation reactor A, acetonitrile is added (Stream (4); chemical class; of 10605 with a purity of about 799.9; contains between 70-180 ppm wt propionitrile 5-20 ppm wt acetamide and < 5 100 ppm wt water as an impurity) optionally to compensate for possible loss of solvent.The actual amount of acetonitrile necessary added was adopted in addition Ag on the loss in outgoing currents by-products but Wiad on the number of samples taken for analysis. A typical amount of acetonitrile added additionally to the design of the process described above can be in the range of 100 to 150 g/hr. 0 Example 1: Regeneration of the catalyst with a one-time titanium-zinc MWW structure Partial regeneration of the catalyst with a titanium-zinc MWW structure was performed based on the epoxidation reaction configuration as described in Reference Example 2 above. The reactor was filled with the catalyst with a MWW-type structure containing titanium and zinc according to Reference Example 1. The epoxide-treated Jeli was run continuously until the selectivity to propylene oxide formation in (a2) based 5 on hydrogen peroxide decreased by 72 with respect to the mean selectivity to Formation of propylene oxide in (2) based on hydrogen peroxide during the first 1,000 hours of the step (a) procedure. Thereupon the

reaction and the reactor was washed free of hydrogen peroxide; Propylene and propylene oxide. after decompression and unloading; The reactor was washed at 70 °C with demineralized water from top to bottom at a vacuum-per-hour fluid velocity of about 7 m/hr (Vph ply over the blank tube cross-section) for at least 3 hours. after this time; The liquid aqueous system exiting the reactor showed a total concentration of organic kreone less than 70.1 of the maximum value detected and the total volume of the liquid aqueous system obtained from the reactor in the scrubbing process was greater than the volume of the reactor. ol The reactor has been discharged and restarted. alii Continuous operation was performed according to reference example 2 and performed for approximately 1500 hours until the reaction temperature again reached its pre-regeneration value. 0 Comparative example 1: Continuous operation according to reference example 2 without renewal as a comparative example; Operation was carried out according to JU Reference 2 for 2,500 hours without catalyst regeneration. Results from Example 1 and Comparative Example 1 The results from Example 1 and Comparative Example 1 are discussed below and shown in Table 1. The inlet medium temperature of the epoxide curing unit A in both Example 1 and Comparative Example 5 1 during continuous operation was set to Reference Example 2 to hold the conversion of hydrogen peroxide essentially constant in a range of 90 to 792 (see Reference Example 2; section 1-1a). The temperature of the heat transfer medium (sla) produced by the epoxide curing unit A after a total runtime of 2,500 hours is given in Table 1 for both Comparative Example 1 and Example 1. Further; Retarding rate is determined as the ratio of the heat transfer medium temperature difference at the inlet at 0 end of trial and beginning of trial divided by the total pu runtime of 2,500 hours; SY is in degrees Celsius/day. Further (Wal) selectivity 5 epoxidation reaction based on hydrogen peroxide after a total run time of 2,500 hours is provided in Table 1. Selectivity / 75 = x (n(PO) / n(H202)) 100 where “ (00) is the molar amount of propylene oxide that dissolved die immediately after unit b and “(E11:0) is the molar amount of hydrogen peroxide that was converted in the epoxidation reaction. Table 1

Er 1 T° after 2.500 hours depending on the current / °C No No EE 0.240 0.2 days as clearly shown in Table 1; The process of the present invention allows the “A” epoxide curing unit to be operated after a total run time of 2,500 hours at a significantly lower cooling water temperature; i.e. the catalyst shows much better performance than in comparative example 1. Moreover; Also, the rate of inhibition (delta (1) / deltal)) is different in the two experiments and is much less than in the inventive example. Furthermore Wad 5 provides the process according to the present invention; having a total runtime of 2,500 hours; Much higher selectivity than in comparative example 1. The catalyst (dad) in Example 1 exhibited a differential conversion temperature of 1 K” where the differential conversion temperature is defined as the absolute difference between (a) the temperature at which hydrogen peroxide-792 is converted 90 when the regenerated catalyst is used as a catalyst; and (b1) the temperature at which said specific hydrogen peroxide was converted to 0 when the corresponding new catalyst was used under other identical epoxidation reaction conditions. Furthermore it; The regenerated catalyst in Example 1 showed a differential selectivity of 70.3 points where the differential selectivity is defined as an absolute difference of 7 points between (ii) the selectivity aly on hydrogen peroxide in an epoxidation process where the regenerated catalyst is used as a catalyst; and (ii) the selectivity Based on hydrogen peroxide in said epoxidation process Cus the corresponding new catalyst is used as a catalyst under other identical epoxidation reaction conditions EXAMPLE 1-2: RENEWING OF THE CATALYST A structure of type MWW containing titanium and zinc according to the invention which includes three washing steps Partial regeneration of the catalyst was performed with a titanium-zinc MWW structure based on a configuration

Epoxidation reaction as described in Reference Example 2 above. Epoxidation Partial regeneration of the catalyst was performed with a titanium-zinc MWW structure based on the epoxidation reaction configuration as described in Reference Example 2 above. The main reactor was catalyst filled with a titanium-zinc MWW structure according to Reference Example 1. The epoxidation reaction was run continuously for approximately 1300 hours until the epoxidation reaction heat "dad" was reached, defined as the temperature of the heat transfer medium at the inlet of the mantle main reactor whose initial value at dy the epoxidation reaction reached 30 °C to a value of 50 °C.At this time point the epoxidation reaction was stopped by stopping the flow of 0 hydrogen peroxide the flow of acetonitrile and propane was resumed until the Then, the reactor was washed to be free of hydrogen peroxide »propylene and propylene oxide by passing a mixture of acetonitrile and water through the reactor (780 by weight of acetonitrile » 720 by weight of water), where the temperature of this mixture reached 50 degrees Celsius This is followed by the draining of a large part of the mixture of acetonitrile and water from the reactor 5 The first washing step After that, the reaction tubes were filled from the bottom with water having a temperature of 70 °C, and then passed Run water having a ha of 70°C from top to bottom through pipes for about 6 hours. Water washing was stopped once the conductivity of the outflow water reached less than 200 μSm. The water was then drained from the reactor. 0 Epoxidation Continuous operation as per Reference Example 2 was resumed and performed for 1400 hours (Goi) until the reaction temperature (da) again reached a value of 50 °C. at this point in time; The epoxidation reaction was stopped by stopping the flow of hydrogen peroxide; The flow of acetonitrile Cg lls was resumed until the end of the epoxidation treatment in the tubes. then; The reactor was washed free of 5 hydrogen peroxide; propylene and propylene oxide by passing a mixture of acetonitrile and water

through the reactor (780 by weight of acetonitrile » 720 by weight of water), where the temperature of this

mixture 50 °C; This is followed by the discharge of a large sha mixture of acetonitrile and water from the reactor.

The second washing step

after that"; The reaction tubes were filled from the bottom with water having a temperature of 70 °C; Then it was done

Passing water which has a temperature of 70°C from top to bottom through pipes for a period of time

about 6 hours. Water flushing was stopped once the conductivity of the water effluent to the outside reached lower

of 200 microns. The water was then drained from the reactor.

Epoxide treatment

Continuous operation as per reference Example 2 was resumed and performed for approximately 1200 hours until 0 reaction temperature again reached a value of 50°C. at this point in time; Interaction has stopped

epoxidation by stopping the flow of hydrogen peroxide; The flow of acetonitrile was excluded

Cg lls until the end of the epoxide treatment in the tubes. then; The reactor was washed to be free of

Hydrogen peroxide » propylene and propylene oxide by passing a mixture of acetonitrile and water

5 through the reactor (780 by weight of acetonitrile » 720 by weight of water), where the temperature of this mixture reached 50 degrees Celsius; This is followed by the draining of a large portion of the mixture of acetonitrile and water from the reactor.

Residual amounts of acetonitrile and water were removed from the reactor by passing nitrogen through a bed

The catalyst is at a nitrogen temperature of 70 °C.

Third washing step

after that; The reaction tubes were filled from the bottom with water having a temperature of 70 °C; Then the water with a temperature of 70°C was passed from top to bottom through the tubes for

about 6 hours. Water flushing was stopped once the conductivity of the water effluent to the outside reached lower

of 200 microns. The water was then drained from the reactor.

calcination step

then; The nitrogen was passed through the catalyst bed for approximately 60 hours at an initial nitrogen 5 temperature of 70 °C at which time this hall temperature was decreased to a value of 100 °C at 10 K/

an hour. after that; The catalyst was calcined by passing a gaseous mixture of air and nitrogen through a bed

catalyst at a flow rate of 0.58 kg/sec. The temperature of said mixture was further decreased continuously at 10 K/hr from its initial value of 100°C to a final value of 450°C and from 25 kept essentially constant at a value of 450°C for 6 hours. At the onset of calcination” the gaseous mixture that is passed into the reactor has an oxygen content of 4 7 by volume. Once it reaches 450°C; The reported oxygen content was set to a value of 21 7

by size. after calcination at 450 °C; The reactor was cooled to a temperature of approximately 30 °C. Epoxide curing Continuous operation as per Reference Example 2 has been resumed and performed for approximately 1000 hours.

0 Example 2-2: Regeneration of the catalyst A titanium-zinc MWW structure of the invention for which partial catalyst renewal is performed with a titanium-zinc MWW structure based on an epoxidation reaction configuration as described in Reference Example 2 above . Epoxide treatment

5 “The main catalyst reactor was filled with a MWW structure containing titanium and zinc according to Reference Example 1. The epoxidation reaction was run continuously for 1200 hours Gs until the ‘Epoxidation Reaction Temperature’” specified as the temperature of the heat degradation medium was reached at the inlet of the main reactor cap whose initial value at the beginning of the epoxidation reaction reached 30 °C; to dad is 50 degrees Celsius. at this point in time; The epoxidation reaction was stopped through

0 turn off the hydrogen peroxide flow; The flow of acetonitrile and propene was resumed until the end of the epoxidation treatment in the tubes. then; The reactor was washed free of hydrogen peroxide; propylene and propylene oxide by passing a mixture of acetonitrile and water through the reactor (780 by weight of acetonitrile »720 by weight of water), where the temperature of this mixture reached 50 degrees Celsius; This is followed by the draining of a large portion of the aceto-joinin mixture and water from the reactor.

5 The first washing step

after that"; The reaction tubes were filled from the bottom with water having a temperature of 70 °C; The water, which has a temperature of 70 degrees Celsius, was then passed from top to bottom through the tubes for about 6 hours. Water washing was stopped once the conductivity of the outflow water reached less than 200 μSm. The water was then drained from the reactor. Epoxide treatment

Continuous operation according to reference example 2 was resumed and performed for approximately 1300 hours until the reaction temperature (da) again reached a value of 50 °C. at this point in time; The epoxidation reaction was stopped by stopping the flow of hydrogen peroxide; The flow of acetonitrile Cg lls was resumed until the end of the epoxidation treatment in the tubes. then; The reactor was washed to be free of

0 hydrogen peroxide; propylene and propylene oxide by passing a mixture of acetonitrile and water through the reactor (780 by weight of acetonitrile »720 by weight of water), where the temperature of this mixture reached 50 degrees Celsius; This is followed by the discharge of a large sha mixture of acetonitrile and water from the reactor. Residual amounts of acetonitrile and water were removed from the reactor by passing nitrogen through the catalyst bed at a nitrogen reagent temperature of 70 °C.

5 The second washing step after that »; The reaction tubes were filled from the bottom with water having a temperature of 70 °C; The water, which has a temperature of 70 degrees Celsius, was then passed from top to bottom through the tubes for about 6 hours. Water washing was stopped once the conductivity of the outflow water reached less than 200 μSm. The water was then drained from the reactor.

0 calcination step then; The nitrogen was passed through the catalyst bed for approximately 60 hours at an initial nitrogen temperature of 70 °C where this temperature was decreased to a value of 100 °C at 10 K/hr. after that; The catalyst was calcined by passing a gaseous mixture of air and nitrogen through the catalyst bed at a flow rate of 0.58 kg/sec. The temperature of the aforementioned mixture decreased continuously

5 further at 10 K/hr from an initial value of 100°C to a final dad of 450°C and from 25 kept essentially constant at a value of 450°C for 6 hours.

At the onset of calcination” the gaseous mixture that is passed into the reactor has an oxygen content of 4 7 by volume. Once it reaches 450°C; The reported oxygen content was adjusted to a value of 21 7 vol. after calcination at 450 °C; The reactor was cooled to a temperature of approximately 30 °C. Epoxide treatment

Calin Continuous operation was performed according to reference example 2 and performed for approximately 1000 hours. Comparative Example 2: Catalyst Regeneration of a Titanium-Zinc-Type MWW Structure Involving Single-Step Epoxidation Washing

0 The catalyst regeneration with a titanium-zinc-aly-type MWW structure is performed on the epoxidation reaction configuration as described in Reference Example 2 above. The main reactor was catalyst filled with a titanium-zinc MWW structure according to Reference Example 1. The epoxidation reaction was run continuously for approximately 2200 hours until the epoxidation reaction temperature “day” specified as the medium temperature was reached at the inlet The main reactor cap hit

5 its initial value at the start of the epoxidation reaction at 30 °C; to a value of 50 °C. at this point in time; The epoxidation reaction was stopped by stopping the flow of hydrogen peroxide; Cl acetonitrile and propene were flowed until the end of the epoxide treatment in the tubes. then; The reactor was washed to WIA of hydrogen peroxide; propylene and propylene oxide by passing a mixture of acetonitrile and water through the reactor (780 by weight of acetonitrile » 720 by weight of

0 water) Cus the temperature of this mixture was 50 °C; This is followed by a large oh discharge of the mixture of acetonitrile and water from the reactor. Residual amounts of acetonitrile and water were removed from the reactor by passing nitrogen through the catalyst bed at a nitrogen reagent temperature of 70 °C. washing step

5 After that, the reaction tubes were filled from the bottom with water having a temperature of 70 °C; The water, which has a temperature of 70°C, was then passed from top to bottom through the tubes for a period of time

about 6 hours. Water washing was stopped once the conductivity of the outflow water reached less than 200 μSm. The water was then drained from the reactor. calcination step then; The nitrogen was passed through the catalyst bed for approximately 60 hours at an initial nitrogen temperature of 70 °C where this temperature was decreased to a value of 100 °C at 10 K/hr. after that; The catalyst was calcined by passing a gaseous mixture of air and nitrogen through the catalyst bed at a flow rate of 0.58 kg/sec. The temperature of the said mixture was further decreased continuously at 10 K/hr from its initial value of 100°C to a final value of 450°C and from 25 kept essentially constant at a value of 450°C for 6 hours. 0 at onset of calcination.” The gaseous mixture passed into the reactor has an oxygen content of 4 7 by volume. Once it reaches 450°C; The reported oxygen content was adjusted to a value of 21 7 vol. after calcination at 450 °C; The reactor was cooled to a temperature of approximately 30 °C. Epoxide 5 Curing Continuous operation per reference example 2 is excluded and performed for approximately 1000 hours. Results from Examples 1-2, 2-2, and Comparative Example 2 The results from Examples 1-2, 2-2, and Comparative Example 2 are discussed below and illustrated in Table 2 below. The inlet temperature of the epoxide curing unit A medium in each of Examples 1-2, 2-2, and Comparative Example 2 during continuous operation was adjusted according to Reference Example 2 to keep the conversion of 0 hydrogen peroxide essentially constant at approximately 7 96 . The selectivity of the 5 hydrogen peroxide based epoxidation reaction (SUIS) provided in Table 2 is defined as x (n(PO) / n(H202) 0 where (POD is the molar amount of propylene oxide that is detected die Immediately after unit B 5 (H2O2)n is the molar amount of hydrogen peroxide converted in the epoxidation reaction.5 Table 2

Example 2.1 | JE Example FES EE Epoxide curing time before washing step | 1300 0 2200 Ohms The epoxide curing time after the washing step 1400 1300 s Epoxide curing time after washing step | 1200 years of epoxide curing time up to | 3900 0 2200 Lan EE selectivity after 1000 hours of calcination / | 97.3 4 | 972 the i as clearly shown in Table 2. The process according to the invention where one washing step (Example 2-2) and two washing steps (Example 2-1) are performed without a subsequent calcination step leads to a slight improvement; However, there is a marked improvement in selectivity (after 1000 hours of calcination) compared to the common process (Comparative Example 2) in which calcination is performed immediately after (and only) the washing step. This surprising result is achieved even though the total epoxidation time up to the calcination step is long (more than 300 lad hours for Example 2-2) or significantly longer (more than 1700 lad hours for Example 1-2) . Thus, it is convincingly evident that the innovative idea of partial regeneration according to stage (1), which works to avoid the calcination step after each washing step and thus; It is a much less complicated process; Unexpectedly leads to more results Lad Baas The most important variable - specifically 0 - relates to the process at an industrial level; That is, selectivity towards products of value. Cited references

International Application No. 55229/98 A1 - 11442 221 1 European Patent No. - International Application No. 000827/2005 A1 - International Application No. 013739/2007 A1 -

Ullmann's Encyclopedia of Industrial Chemistry, 5 edition, volume 13, p. 447-456 = 5

Atlas of Zeolite Framework Types, 5% edition, Elsevier, London, England (2001) — US Patent No. 112007043226 - US Patent No. 601146551 -

Wau et al., “Hydrothermal Synthesis of a novel Titanosilicate with MWW Topology”, -

Chemistry Letters (2000), p. 774-775 0 211175362013 International Application No. - Sequence List:

TL "fr

BL "b".

Claims (1)

protection elements 1. Process for catalyst regeneration comprising titanium-containing zeolite for MWW framework structure as active material (Gia active material) comprising (1) stage comprising 0 continuous preparation of propylene oxide Jaa (1 f) 5 feed stream comprising cpropene hydrogen peroxide or chydrogen peroxide source and organic solvent in reactor contains catalyst comprising zeolite containing titanium a gti) for MWW framework structure as active material catalyst; (2) Subjecting the feed stream according to (17) in the reactor to epoxidation 0 conditions in the presence of the catalyst, which results in obtaining a reaction mixture comprising propylene oxide (plug yl!) and the organic solvent. torganic solvent f) 3) remove a product stream comprising propylene oxide and organic solvent from the ¢reactor (b) stop feeding the feed stream into the reactor treactor 5 (c) dud catalyst in catalyst containing reactor Sle liquid aqueous system containing 7100-95 wt sla cele on total system weight el liquid aqueous system where washing takes place for 2 to 12 hours; Phase (1) also includes repeating the sequence of steps (a) to (c) “times where” he is an integer from 1 to 10; process for regeneration also includes 0 Phase (1) also includes repeating the sequence of steps ( to (c) “times where” is an integer between 1-10; a regeneration process that also includes (2) a stage comprising the calcination of the catalyst obtained from (c) after repeating the sequence of steps 0 to ( c) “times” where the calcination is performed at a temperature of the catalyst in the range from 300 to 600 °C using a gas stream comprising oxygen 25 in the reactor containing the catalyst; where the sequence of stages (1) to (2) Siem is optionally repeated where m is an integer between 1-10; 2. Process under claim 1; Cua the organic solvent is methanol 5 or acetonitrile . 3. The process according to claim 1 or 2 where 7100-99 by weight of the framework structure of the zeolite containing titanium for the framework structure MWW consists of silicon titanium and oxygen 10 4 process under claim 1; The titanium-containing zeolite with the MWW framework structure contains zinc (70). 5. Operation according to protection 1 pale; The catalyst comprising titanium-containing zeolite embedded in the MWW framework structure is present in the reactor as a fixed-bed dul bed catalyst. .catalyst 6. Operation Cua] The offshore liquid aqueous system according to (c) contains 7100-99.9 wt cele based on the total weight of the liquid aqueous system | 0 7. Process under claim 1; Where according to (c); The catalyst is washed into the reactor containing the catalyst in a continuous pattern. 8. Process according to claim 7 Cus the reactor according to 0 is a tube reactor or ela] ug tube bundle reactor washing according to (c) with the help of the system liquid aqueous system at liquid hourly space (LHSV) velocity in the range of 1 to 20 m/h. 9. process under claim 1; Where the washing is carried out according to (C) at a temperature of the liquid aqueous system 5 in the range from 30 to 90 °C. 0. process under claim 1; Where the washing is carried out according to (c) until the total organic carbon concentration in the liquid aqueous system after contact with the catalyst is at most 75 of the maximum total organic carbon concentration detected 0 during washing in (c). 1. The process according to claim 1 » where the sequence of steps (b) (z)s is completed when the selectivity of the epoxidation reaction according to (21) decreases by 74 or less relative to the average selectivity of the epoxidation reaction reaction Souls according to 02 within the first 100 hours of the step 0 procedure, where the selectivity of the epoxidation reaction is defined as the molar amount of propylene oxide obtained in (21) relative to the molar amount of peroxide The hydrogen peroxide that was converted in (2). 2. process under claim 1; where “ is in the range of 1 to 6. 3. process under claim 1; The calcination is carried out according to stage (2) at a catalyst temperature in the range of 350 to 550°C. 4. The process according to Claim 1 where the sequence of phases (1) to (2) chem is repeated so that 5 is “an integer number in the range from 1 to 6. 5. Continuous process for the preparation of Glug ll 00071608 oxide incl age(1) includes f) Continuous preparation of propylene oxide (lug yall) First reactor incorporating (AD) Input feed stream comprising cpropene hydrogen peroxide Hydrogen peroxide or source of hydrogen peroxide and organic solvent organic solvent 5 first reactor containing catalyst containing Zeolite containing titanium for MWW framework structure as an active material catalytic material (2) Subjecting the feed stream according to (A1) in the first reactor to epoxide treatment conditions. epoxidation in the presence of the catalyst, resulting in a reaction mixture comprising 0 propylene oxide (plug yl!) and a torganic solvent organic and organic solvent propylene oxide Remove product stream containing propylene oxide (3 f) solvent from the first reactor; (b) stop feeding the feed stream to the first reactor; (c) Washing of the catalyst in the reactor containing the catalyst with a liquid aqueous system 5 containing 7100-95 by weight cele based on the total weight of the liquid aqueous system Cus 110010 aqueous system is flushed for 2 to 12 hours; Phase (1") also includes repeating the sequence of steps (Cz) (CT) '" times such that '' is for a whole number from 1 to 10; The propylene oxide preparation process also includes: (72) stage comprising the calcination of the catalyst obtained from (Cr) after repeating a sequence of steps 0) to (Tz) ‘‘times’ where calcination is performed at a temperature of the catalyst in Range from 300 to 600 °C using a gas stream that includes oxygen tcatalyst in the reactor containing the oxygen catalyst where optionally the phase sequence hem’ (U2) (CL) is repeated such that !00 is a number true and between 1-10; where in each iteration of the sequence of steps (1”) to (2); similar to “or different; The propylene oxide preparation process also includes: (1) Stage comprising 0) Continuous preparation of propylene oxide (lug in a second reactor comprising f) 1) Introducing a feed stream comprising 0©0200proylene; hydrogen peroxide peroxide source of hydrogen peroxide chydrogen peroxide and organic solvent 5 the second reactor containing the catalyst containing zeolite containing titanium for a framework structure MWW as a material active material dads catalysts; f) 2) subjecting the feed stream according to “A1” in the second reactor to epoxidation conditions in the presence of the catalyst, which leads to obtaining on a reaction mixture comprising propylene oxide and organic solvent 'ab) (a3) 0 product stream comprising propylene oxide and organic solvent from reactordeliall II; (b) stop feeding the feed stream into the second reactor; (c) wash the catalyst in the catalyst containing reactor alyst with SLE liquid aqueous system containing 95-7100 by weight water; Based on the total weight of the aqueous system 5 Lunduna washing for 2 to 12 hours; Stage (71) also includes repeating the sequence of steps (a) to (c) ““ times so that “0” is an integer number from 1 to 10; the propylene oxide preparation process also includes (2) stages Comprising the calcination of the catalyst obtained from (c") after repeating the sequence of steps (a") to (c) cian" where the calcination shal takes place at a catalyst temperature in the range of 0 300 to 600 °C using a gas stream containing oxygen the reactor containing the catalyst optionally repeating the sequence of phases (1) to (2) 7” times such that “0” is Ble for an integer between 1-10) where in each iteration of the sequence of steps (1”) to (2”); c') and (2'); Gis propylene oxide (a”) is prepared. > =" nw z = 1 1 | N : z ا . 2 - 2 - CTY sib - . 9 ha 2 say b ay 0 lac ( lahj | 221 hod 1 Do 1 : : Support : PY wu pet = : & : 3 1 pans b J button . "m = i a d 3 pee + = _ - = ks 1 Fig. a a ag a 2 ; Les led Ea 2 x 7 3 ay airy fos = Ea 5e wg ab J od Mei BE Zo A F | i Bs : w © 3 Aan _ BAN FX oF = i TE Ye) 1 rb 0 Figure? Sued Authority for Intellectual Property RE .¥ + \ A 0 § 8 Ss o + < M SNE A J > E K J TE I UN BE Ca a a a ww > Ld Ed H Ed - 2 Ld, provided that the annual financial consideration is paid for the patent and that it is not null and void for violating any of the provisions of the patent system, layout designs of integrated circuits, plant varieties and industrial designs, or its implementing regulations. Ad Issued by + bb 0.b The Saudi Authority for Intellectual Property > > > This is PO Box 1011 .| for ria 1*1 v= ; Kingdom | Arabic | For Saudi Arabia, SAIP@SAIP.GOV.SA