TW509694B - Improved metal-ligand complex catalyzed processes - Google Patents

Abstract

This invention relates to a process for separating one or more phosphorus acidic compounds from a reaction product fluid containing said one or more phosphorus acidic compounds, a metal-organophosphite ligand complex catalyst and optionally free organophosphite ligand which process comprises (a) treating said reaction product fluid with water sufficient to remove at least some amount of said one or more phosphorus acidic compounds from said reaction product fluid and (b) treating the water which contains phosphorus acidic compounds removed from said reaction product fluid with an acid removal substance sufficient to remove at least some amount of said one or more phosphorus acidic compounds from said water.

Description

509694 A7 B7 V. Description of the invention (彳 Scope of the invention) The present invention relates to an improved method of metal-organophosphite complex catalysis. More specifically, the present invention relates to the use of one or more acid shifts. Removal of substances to remove phosphoric compounds formed in a method catalyzed by metal-organophosphite complexes, and to prevent and / or reduce the hydrolytic degradation of organophosphite ligands, and such Method for the inactivation of metal organic phosphite coordination dislocation catalysts. Chunming background is known in the art. Different products can be reacted in the presence of metal-organic acid vinegar coordination dislocation catalysts through reactions. One or more reactants. However, the stabilization of catalysts and organophosphite ligands is still a major concern in this technology. Obviously, catalyst stability is one of the most important when using any catalyst. Key issues. The loss of catalyst or catalytic activity due to the undesired reaction of highly precious metal catalysts may be detrimental to the manufacture of the desired product. Similarly, the organic compounds used during the manufacturing process Degradation of the ester ligands may lead to poisoned organic phosphite compounds or inhibitors or acidic by-products, which will reduce the catalytic activity of the metal catalyst. Furthermore, when the productivity of the catalyst decreases, the production of the product The cost will obviously increase. For example, 'metal-organic phosphite: acid-vinegar coordination complex catalyzed by gas formication method of organic phosphite ligand degradation and catalyst inactivation is a major reason The hydrolysis instability of phosphate ligands. All organic phosphites are more or less easily hydrolyzed. The hydrolysis rate of organic phosphites is usually determined by the stereochemical properties of organic phosphites. Generally this paper size Applicable to China National Standard (CNS) Α4 specification (210X297 mm) Please read the back I, the matter, the item, and then the page on this page. Ordered by the Central Consumers Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperatives 509694 A7 B7 V. Description of the invention (2) In terms of the larger the three-dimensional environment surrounding the phosphorus atom, the slower the hydrolysis rate. For example, 'tertiary triorganophosphite, such as triphenylphosphite, For example, the two organic phosphites disclosed in U.S. Patent No. 4,737,588 are more easily hydrolyzed than the organic polyphosphites disclosed in U.S. Patent Nos. 4,748,261 and 4,769,498. Furthermore, all such hydrolysis reactions are unchanged A phosphoric acid compound is generated which catalyzes the hydrolysis reaction. For example, the hydrolysis of a tertiary organic sulfite will produce a phosphonic acid diester that can be hydrolyzed to a phosphonic acid monoester, which in turn can be hydrolyzed to h3po3 acid. Furthermore, the hydrolysis of by-products of side reactions, such as between phosphonic diesters and aldehydes, or between some organic phosphite ligands and acids, may lead to the production of undesired strong aldol acids, For example η-ί: 3Η7αΗ (; ΟΙί) Ρ⑼. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) In fact, 'Even if it is not highly hydrolyzable, The essential three-dimensional hindering organic diphosphite will also react with the aldehyde product to form a poisoned organic phosphite, such as an organic monophosphite, which is not only a catalytic inhibitor, but also extremely easy Hydrolysis, the formation of such uronic acid by-products, such as hydroxyalkylphosphonic acids, is shown, for example, in U.S. Patents 5,288,918 and 5,364,95 °. Furthermore, in view of the hydrolysis of the organic phosphite ligands, in view of such phosphoric compounds such as ma? 〇3, the production of uronic acid such as hydroxyalkylphosphonic acid h3P〇4 and the like, so it can be considered as autocatalytic, and if left unchecked, this continuous liquid cycle hydroformylation method The catalyst system will become more and more acidic sooner or later. Therefore, the unacceptable amount of this phosphonium acidic substance accumulated in the end may cause the complete destruction of the existing organic phosphite vinegar, so that the hydroformylation catalyst is completely ineffective (deactivated) and valuable. The germanium metal is easy to lose, for example, due to the paper size on the reaction sheet, Gu Jiaguan (iNS) A4 specification (509694 A7 B7) 5. Description of the invention (3) and / or deposition. Accompanying the hydroformylation method Another problem is related to metal salt contamination. See, for example, U.S. Patent No. 4,143,075. Metal salt contaminations such as iron, zinc, calcium salts, etc. in the tomazanization reaction product fluid can promote the autolysis of acids. Condensation. Such undesired aldehyde condensation products, including aldol condensation products, from the viewpoint of molecular weight, its molecular weight range is changed from dimer structure to tetramer structure and larger. Therefore, a kind of prevention and / or reduction A successful method for such hydrolytic degradation and catalyst inactivation of organic sub-transesterate ligands is highly desirable for this technology. Disclosure of the Invention Central Bureau of Standards, Ministry of Economic Affairs Printed by an employee consumer cooperative (please read the notes on the back before filling out this page) It has now been found that one or more acids can be used to remove substances such as metal oxides, scandium oxides, carbonates and / or carboxylates, In order to effectively remove such phosphoric compounds, and thus prevent and / or reduce the hydrolytic degradation of organic phosphite ligands that may occur during processes using metal-organophosphite coordination dislocation catalysts and Inactivation of metal-organic phosphite coordination catalysts. It has been found that we can take advantage of the acidity removal ability of certain acid removal substances and transfer a minimum of metal salts to the reaction product fluid. It has also been surprisingly found The smallest loss of the organic phosphite ligand occurs when the reaction product fluid containing the metal-organic phosphite coordination catalyst is in contact with an acid-removing substance, or in contact with water, and then the contacted When the water is treated with an acid-removing substance, even at high temperatures, the present invention relates in part to a catalyst and a catalyst containing a complex dislocation containing one or more phosphoric acid compounds and metal-organic phosphites. Free state of choice ____________-6-This paper size applies to China National Standard (CNS) A4 (210X297 mm) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 509694 Μ _ Β7 --------- ----------- -----............--------------_ w 5. Description of the invention (4) Organic phosphite compound A method for separating the one or more rhenium compounds from a reaction product fluid of a site 'this method includes treating the reaction products with water sufficient to remove at least some amount of the one or more phosphoric compounds from the reaction product fluid Fluid, and (b) treating the water 'containing the bricky acidic compound removed from the reaction product fluid with an acid removal substance sufficient to remove at least some amount of the one or more phosphoric acid compounds from the water. The invention also relates in part to a stabilization method for making an organic phosphite ligand resistant to hydrolytic degradation and / or a metal-organic squatate coordination complex catalyst to resist inactivation. The method comprises Remove at least some amount of water of one or more phosphorous compounds from the reaction product fluid, and treat the metal-organophosphite coordination dislocation catalyst and optionally the free-state organic phosphite ligand and also contain A reaction product fluid of one or more phosphoric compounds, and (b) water containing phosphoric compounds removed from the reaction product fluid, using a sufficient amount to remove at least some amount of the one or more phosphoric compounds from the water. Acid removal material treatment. The invention further relates to a method for preventing and / or reducing the hydrolytic degradation of the organic phosphite ligand and / or the deactivation of the metal-organophosphite coordination catalyst, the method comprising (a) Use water sufficient to remove at least some amount of one or more phosphoric acid compounds from the reaction product fluid to treat metal-organic phosphinic acid g complex coordination catalysts and optionally free state organic phosphite coordination The reaction product fluid that also contains one or more phosphoric acid compounds, and (b) water containing phosphoric acid compounds removed from the reaction product fluid, using at least some amount of the one or more water sufficient to remove the water Treatment of phosphoric acid-removing substances. This paper size is applicable + MinShan Han (CNS) A4 specification (210X297 / mm) 1------ (Please read the precautions on the back before filling this page)

509694 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (5) The present invention further relates to an improved method, which includes the metal-organic phosphorous acid vinegar coordination mismatch catalyst and optional Reacting one or more reactants in the presence of a free-state organic phosphite ligand to produce a reaction product fluid containing one or more products, improvements including preventing and / or reducing any of the organic phosphite ligands Hydrolytic degradation and deactivation of the metal-organophosphite coordination catalyst by using an acid-removing substance sufficient to remove at least some amount of phosphoric acid compound from the reaction product fluid Processing at least a portion of a reaction product fluid derived from the method and also containing phosphoric compounds formed during the method. The present invention also relates in part to an improved method for making one or more products, including (i) at least In a reaction zone, in the presence of a metal-organic transesterate coordination dislocation catalyst and optionally a free-state organic transesterate ligand, Reacting one or more reactants to produce a reaction product fluid comprising one or more products, and (ii) separating one or more products from the reaction product fluid in or in at least one reaction zone The improvement matters include preventing and / or reducing any hydrolytic degradation of the organic phosphite ligand and the inactivation of the metal-organophosphite coordination dislocation catalyst by (a) at least one In the scrubbing zone, use water sufficient to remove at least some amount of the phosphoric acid compound from the reaction product fluid, to treat at least a portion of the reaction product fluid derived from the method and also containing acidic compounds riding during the method, And (b) in at least one acid removal zone, at least a portion of the water containing the phosphoric acid compound removed from the reaction product fluid is used to remove at least some amount of the phosphoric acid compound from the water-- -----— 8 > --_ (Please read the notes on the back before filling this page)

Use appropriate ruled paper, winter standard, national calendar, and national calendar. 7 509694 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. A further part of the present invention relates to an improved method for manufacturing one or more products, including (i) in at least one reaction zone, a metal-organic phosphite coordination dislocation catalyst and optionally a free-state organic Reacting one or more reactants in the presence of a phosphate ligand to produce a reaction product fluid comprising one or more products, and (ii) in at least one separation zone or in the at least one reaction zone, from The reaction product fluid separates one or more products, and improvements include preventing and / or reducing any hydrolytic degradation of the organic phosphinate ligand and inactivation of the metal-organophosphite coordination dislocation catalyst, This is accomplished by treating, in at least one acid removal zone, one or more acid removal substances sufficient to remove at least a number of phosphoric compounds from the reaction product fluid, treating at least a portion of the process derived from the method and also containing The reaction product fluid of the phosphoric acid compound formed during the process causes the processed reaction product fluid to return to the at least one reaction zone or the at least one separation zone. The present invention further relates to an improved method for manufacturing one or more products, which includes (i) in at least one reaction zone, a metal-organophosphite coordination catalyst and a free-state organic compound selected as appropriate Reacting one or more reactants in the presence of a phosphite ligand to produce a reaction product fluid comprising one or more products, and (ii) in at least one separation zone or in the at least one reaction zone, from The reaction product fluid separates one or more products, and the improvement matters include preventing and / or reducing any hydrolytic degradation of the organic phosphite ligand and inactivation of the metal-organophosphite coordination dislocation catalyst, The method is: (a) In at least one scrubbing zone, use __________ This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) Equipment-, tr Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 509694 A7 -_-—__ B7 V. Description of the invention (7) Remove at least some amount of water of phosphoric acid compounds from the reaction product fluid. Processing at least a portion of the reaction product fluid derived from the process and also containing phosphoric compounds formed during the process, (b) returning the processed reaction product fluid to the at least one reaction zone or the at least one separation zone In the at least one acid removal zone of U, use one or more acid-removing substances sufficient to remove at least some amounts of phosphoric compounds from the water, and treat at least a portion of the Water of the phosphoric acid compound, and ⑼ return the treated water to the at least one scrubbing zone. The present invention also relates in part to an improved method for manufacturing one or more products, including (i) in at least one reaction zone, a metal-organic phosphite coordination catalyst and a free-form organic Reacting one or more reactants in the presence of a phosphate ester ligand to produce a reaction product fluid comprising one or more products, and osmium in the at least one separation zone or in the at least one reaction zone, from the reaction The product fluid separates one or more products, and improvements include preventing and / or reducing any hydrolytic degradation of the organic phosphorous acid g ligand and inactivation of the metal-organic phosphinate coordination dislocation catalyst, This is done by taking at least one reaction zone or the at least one separation zone, taking out at least a portion of the reaction product fluid derived from the process and also containing the acid-transforming compounds formed during the process, (b) at least Treatment of at least a portion of an acid-removing zone derived from the method using one or more acid-removing substances sufficient to remove at least a number of phosphoric compounds from the reaction product fluid And also contains the removed reaction product fluid of the phosphoric acid compound formed during the method, and (c) returns the processed reaction product fluid to the at least one reaction zone or the at least one separation zone, and (d) visual Love ______- 40 -............-............ This paper size applies to Chinese national standards ( CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling out this page) [Package., 11 509694 Printed by A7 B7, Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Disclosure of the invention (8) One or more acids remove the substance. The invention further relates to an improved method for manufacturing one or more products, which includes (i) in at least one reaction zone, a metal-organic phosphite coordination catalyst and a free-state organic Reacting one or more reactants in the presence of a phosphate ligand to produce a reaction product fluid comprising one or more products, and osmium in the at least one separation zone or in the at least one reaction zone from the reaction Product fluid separation of one or more products. Improvements include preventing and / or reducing the hydrolytic degradation of any of the organic phosphite ligands and the inactivation of the metal-organophosphite coordination catalyst. Is to take out at least a portion of the reaction zone or the at least one separation zone, take out at least a portion of the reaction product fluid derived from the process and also containing phosphoric compounds formed during the process, (b) at least one wash In the gas zone, use water sufficient to remove at least some of the scale acidic compounds from the reaction product fluid, treating at least a portion of the process derived from this method and also containing The reaction product fluid of the phosphoric acid compound formed during the extraction is (c) the processed reaction product fluid is returned to the at least one reaction zone or the at least one separation zone, and (d) from the at least one scrubbing zone Taking out at least a portion of the water containing the transacidic compound removed from the reaction product fluid, (e) using at least one acid removal zone in at least one acid removal zone to remove at least some amount from the water; Acid removal material for acidic compounds, treating at least a portion of the extracted water containing phosphoric acid compounds removed from the reaction product fluid, (f) returning the treated water to the at least one scrubbing zone, and ( g) optionally replace the one or more acid removal substances. The present invention further relates to an improved method for manufacturing one or more products. _______ -11 '____ ___ This paper size is applicable to the Chinese National Standard (CNS) A4 specification (2x0297 mm) ----— ^ — I, --- Shang-- (Please read the notes on the back before filling out this page) Order 509694 A7 B7 Five invention descriptions (9, which includes (i) in at least one reaction zone, in metal-organic In the presence of a coordination mismatch catalyst and optionally a free-state organic phosphite ligand, react one or more reactants' to produce a reaction product fluid containing one or more products, and ⑻ in at least one separation zone Or in the at least one reaction zone, one or more products are separated from the reaction product fluid, and improvements include preventing and / or reducing the hydrolytic degradation of any of the organic phosphite ligands and the metal-organic Deactivation of the cyclamate coordination catalyst by introducing in the at least one reaction zone and / or the at least one separation zone sufficient to remove at least some amount of phosphoric acid compound from the reaction product fluid One or more An acid-removing substance that treats at least a portion of a reaction product fluid derived from the method and also containing a hydrazone acidic compound formed during the method. The present invention also relates in part to an improved method for making one or more products, including ( i) In at least one reaction zone, react one or more reactants in the presence of a metal-organotransacid complex coordination catalyst and optionally a free-state organic phosphite ligand to Generating a reaction product fluid comprising one or more products, and (ii) separating one or more products from the reaction product fluid in or in at least one separation zone, improvements including preventing and / Or reduce any hydrolytic degradation of the organic sulfite ligand and the inactivation of the metal-organophosphite coordination catalyst by (a) by introducing sufficient amounts from the reaction product fluid Remove at least some amount of water of the phosphoric acid compound into the at least one reaction zone and / or the at least one separation zone, and treat at least a portion derived from the method and also contained in the method Reaction product stream of phosphoric acid compounds formed between them ----- -12 The paper size of this drawing paper is applicable to the Chinese National Standard (CNS) A4 rule;)) One ~ ----- (Please read the precautions on the back before filling in this Page) [Printed by the Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs, printed 509694 A7 V. Description of the invention (10-body, and (b) In at least one acid removal zone, at least a part of the product containing the reaction product fluid The phosphoric acid compound removed from the water should be treated with an acid removal substance sufficient to remove at least a certain amount of phosphoric acid compound from the water. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (Fill in this page) The present invention further relates to an improved method for manufacturing one or more products, which includes (i) in at least one reaction zone, a metal-organic phosphorous acid vinegar coordination dislocation catalyst and optionally used Reacting one or more reactants in the presence of a free-state organic phosphite ligand to produce a reaction product fluid comprising one or more products, and dysprosium in at least one separation zone or in the at least one In the application zone, one or more products are separated from the reaction product fluid. Improvements include preventing and / or reducing the hydrolytic degradation of any of the organic phosphite ligands and the metal-organic phosphite coordination The inactivation of the hybrid catalyst is performed by (a) taking at least a portion of the reaction zone or the at least one separation zone, at least a portion of which is derived from the method and also contains a riding acid compound formed during the method The reaction product fluid, (b) in at least one scrubbing zone, use at least enough water to remove at least some amount of brick acidic compounds from the reaction product fluid, to treat at least a portion of the process derived from and also contained in the process The reaction product fluid of the phosphoric acid compound formed during the extraction, (c) returns the processed reaction product fluid to the at least one reaction zone or the at least one separation zone, (d) in at least one scrubbing zone, Water containing phosphoric acid compound removed from the reaction product fluid, using one or more acid removal substances sufficient to remove at least some amount of phosphoric acid compound from the water And one or more acid-removing substances as appropriate. The present invention relates in part to a paper containing one or more phosphoric compounds, — «-______- 13- —-------- Applicable to Chinese National Standard (CNS) A4 specification (2ί〇X297 mm) 509694 Printed by A7 B7, Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (Ή) Metal-organic phosphite coordination catalyst and optional use A method for separating the one or more phosphate compounds from a hydroformylation reaction product fluid of a free-state organic phosphite ligand, the method comprising (a) using a sufficient amount to remove from the hydroformylation reaction product fluid At least some amounts of the water of the one or more phosphoric acid compounds are used to treat the hydroformylation reaction product fluid, and the water used to contain the phosphoric acid compound removed from the hydroformylation reaction product fluid is sufficient to be used from the The water removes at least some amount of the acid-removing substance of the one or more phosphate compounds. The invention also relates in part to a stabilization method for making an organophosphite ligand resistant to hydrolytic degradation and / or a metal-organophosphate coordination dislocation catalyst resisting inactivation. The method includes the use of Removal of at least some amount of one or more phosphate compounds from the hydroformylation reaction product fluid, treatment of metal-organophosphite coordination dislocation catalysts and optionally free-state organic phosphite ligands And a hydroformylation reaction product fluid that also contains one or more phosphoric acid compounds, and water that contains phosphoric acid compounds removed from the hydroformylation reaction product fluid, using at least enough to remove at least some of the water An amount of the acid-removing substance of the one or more phosphate compounds is treated. The present invention further relates to a method for preventing and / or reducing the hydrolytic degradation of the organic phosphite ligand and / or the inactivation of the metal-organic acid sulfite coordination dislocation catalyst, the method comprising (a ) Use a water sufficient to remove at least some amount of one or more phosphoric compounds from the hydroformylation reaction product fluid, treat the free organic compounds containing metal-organic phosphite coordination catalysts and use them as appropriate Riding ester ligands also contain one or more phosphoric acid. The paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page).

1.1T printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 509694 A7 ______ B7 V. Description of the invention (12) The hydroformylation reaction product fluid of the sex compound will be removed from the fluid containing the product from the hydration reaction The water of the phosphoric acid compound is treated with an acid removal substance sufficient to remove at least some amount of the one or more phosphoric acid compounds from the water. The invention further relates to an improved method of hydroformylation, which comprises the presence of a metal-organophosphite coordination dislocation catalyst and optionally a free-state organic phosphite ligand, One or more olefinically unsaturated compounds are reacted with carbon monoxide and hydrogen to produce a reaction product fluid containing one or more aldehydes. Improvements include preventing and / or reducing the hydrolytic degradation of any of the organic phosphite ligands and the Deactivation of metal-organic phosphite coordination catalysts by treating at least a portion of the phosphate-derived compound with one or more acid-removing substances sufficient to remove at least a number of phosphoric compounds from the reaction product fluid The hydroformylation process also contains a reaction product fluid of a phosphoric acid compound formed during the hydroformylation process. The present invention also relates in part to an improved hydroformylation method for manufacturing one or more aldehydes, which includes (i) in at least one reaction zone, a metal-organophosphite complex dislocation catalyst and optionally Reacting one or more alkylene unsaturated compounds with carbon monoxide and hydrogen in the presence of a selected free-state organic phosphite ligand to produce a reaction product fluid containing one or more acids, and (ii) in at least one separation zone In the zone or in the at least one reaction zone zone, one or more aldehydes are separated from the reaction product fluid, and improvements include preventing and / or reducing the hydrolytic degradation of any of the organic phosphite ligands, and the metal -The inactivation of the organic phosphite coordination catalyst is carried out in at least one scrubbing zone and is removed from the reaction product fluid to -15.-This paper applies Chinese national standards (CNS ) A4 size (210X297mm) (Please read the notes on the back before filling this page)

、 1T 509694 A7 --------- B7 V. Description of the invention (13)-(Please read the precautions on the back before filling this page) A small amount of water of phosphoric acid compounds, treat at least a part of the water derived from the A reaction product fluid comprising a formazan process and also containing a phosphoric compound formed during the hydroformamation process, which contains phosphoric acid removed from the reaction product fluid in at least one acid removal zone Compound water is treated with a removal substance sufficient to remove at least some amount of a phosphoric compound from the water. A further part of the present invention relates to an improved hydroformylation method for manufacturing one or more aldehydes, which comprises (i) in at least one reaction zone, a metal-organic hypochlorous acid complex coordination catalyst and a video The free organic organic arsonite is selected for the case to 'react one or more olefinic unsaturated compounds with carbon oxide and gas' to produce a reaction product fluid containing one or more acids, and (ii) In at least one separation zone or in the at least one reaction zone, the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs prints one or more aldehydes separated from the reaction product fluid, and improvements include preventing and / or reducing any such Hydrolytic degradation of the organic phosphite ligand and the inactivation of the metal-organophosphite coordination dislocation catalyst by (a) using at least one self-reaction product in at least one removal zone The fluid removes at least some amount of one or more acid-removing substances of a phosphoric compound, and processes at least a portion of the phosphorylated compound derived from the hydroformylation process and also containing the phosphorylated compound formed during the hydroformylation process And (b) returning the processed reaction product fluid to the at least one separation zone or the at least one reaction zone. The invention further relates to an improved hydroformylation method for manufacturing one or more aldehydes, which comprises (i) in at least one reaction zone, a metal-organic phosphite coordination dislocation catalyst and a video Free organic phosphorus in the case ___- 1R -___________ ____ This paper size applies to Chinese National Standard (CNS) A4 (21GX297 mm) 509694 A7 B7 V. Description of the invention (14) In the presence of acid-vinegar ligands' Reacting one or more dilute unsaturated compounds with carbon monoxide and tritium to produce a reaction product fluid comprising one or more aldehydes, and (ii) in at least one separation zone or in the at least one reaction zone, from The reaction product fluid separates one or more acids, and improvements include preventing and / or reducing any hydrolytic degradation of the organic phosphite ligand, and inactivation of the metal-organophosphite coordination dislocation catalyst. By (a) treating at least a portion of the hydroformylation process in at least one scrubbing zone with water sufficient to remove at least some amount of phosphoric acid compound from the reaction product fluid, and A reaction product fluid that also contains a phosphate compound formed during the hydroformylation process, (b) returning the processed reaction product fluid to the at least one reaction zone or the at least one separation zone, (e) at least In an acid removal zone, at least a portion of the water containing the transacid compound removed from the reaction product fluid is used with one or more acid removal substances sufficient to remove at least some amount of phosphoric acid compound from the water Treating, and (d) returning the treated water to the at least one scrubbing zone. Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page). The present invention also relates in part to an improved hydroformylation method for the production of aldehydes, which includes (i) In the reaction zone, one or more olefin unsaturated compounds are reacted with carbon monoxide and hydrogen in the presence of a metal-organic phosphite coordination catalyst and optionally a free-state organic phosphite ligand, To produce a reaction product fluid containing one or more aldehydes, and to separate one or more aldehydes from the reaction product fluid in or in at least one separation zone, improvements including preventing and / Or reduce the hydrolytic degradation of any of the organic phosphite ligands and the inactivation of the metal-organophosphite complexation catalyst, by means of this-__- 17- _____ this paper Standards apply to Chinese National Standard (CNS) A4 specifications (210X297 mm) 509694 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (15) At least one reaction zone or the least A separation zone, taking at least a portion of the reaction product fluid derived from the hydroformylation process and also containing phosphoric compounds formed during the hydroformylation process, (b) in at least one acid removal zone In the belt, one or more acid-removing substances sufficient to remove at least some amounts of transacidic compounds from the reaction product fluid are treated, and at least a portion derived from the hydroformylation process is also contained The removed reaction product fluid of the phosphoric acid compound formed during the process, (C) returns the processed reaction product fluid to the at least one reaction zone or the at least one separation zone, and (d) optionally replaces the one or more acids Remove material. A further part of the present invention relates to an improved hydroformylation method for producing aldehydes, which comprises (i) in at least one reaction zone, a metal-organophosphite coordination dislocation catalyst and optionally selected Reacting one or more hydrocarbon unsaturated compounds with carbon monoxide and argon in the presence of a free-state organic subcasting acid amidine ligand to produce a reaction product fluid containing one or more acids, and (ii) in at least one separation zone In the zone or in the at least one reaction zone zone, one or more aldehydes are separated from the reaction product fluid, and improvements include preventing and / or reducing the hydrolytic degradation of any of the organic phosphite ligands, and the metal -The inactivation of the organophosphite coordination dislocation catalyst by (a) taking at least a portion of the at least one reaction zone or the at least one separation zone derived from the tomazanization method and A reaction product fluid that also contains phosphoric compounds formed during the hydroformylation process, (b) in at least one scrubbing zone, using at least a sufficient amount of phosphoric acid to be removed from the reaction product fluid Water for the treatment of at least a part of the -18 derived from the hydroformylation process and also containing phosphoric compounds formed during the hydroformylation process-This paper is in accordance with China National Standard (CNS) A4 specifications (210X297mm) — ^, n binding ^ (Please read the precautions on the back before filling this page) Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 509694 A7 B7_ _ V. Description of the invention (16) After taking out the response Product fluid, so that the processed reaction product fluid is returned to the at least one reaction zone or the at least one separation zone, (d) taking out at least a portion of the water from the at least one scrubbing zone, which contains water from the reaction Phosphate compounds removed from the product fluid, at least one acid removal zone, using one or more acid removal substances sufficient to remove at least some amount of phosphate compounds from the water, treating at least a portion of the Water containing phosphoric acid compounds removed from the reaction product fluid, ① returning the treated water to the at least one scrubbing zone 'and (g) optionally replacing the one or more Acid removes substance. The invention further relates to an improved hydroformylation method for manufacturing one or more aldehydes, which comprises (i) in at least one reaction zone, a metal-organic phosphite coordination dislocation catalyst and a video In the presence of a free-state organic phosphite ligand, one or more olefinically unsaturated compounds are reacted with carbon monoxide and hydrogen to produce a reaction product fluid containing one or more acids, and (ii) in at least one separation zone In the belt or in the at least one reaction zone, one or more acids are separated from the reaction product fluid, and improvements include preventing and / or reducing the hydrolytic degradation of any of the organic linoleate ligands and the metal- The inactivation of the organic phosphite coordination catalyst includes improvements to prevent and / or reduce any hydrolytic degradation of the organic phosphite ligand, and the metal-organophosphate coordination mismatch. The catalyst is deactivated by introducing into the at least one reaction zone and / or the at least one separation zone enough to remove at least one of the acidic compounds from the reaction product fluid or An acid-removing substance that treats at least a portion of the derivative derived from the hydroformylation process and also contains I ----- · --pack ------ order- ----- (Please read the notes on the back before filling this page) -19- Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 509694 A 7 _B7_ V. Description of the invention (17) Reaction product fluid of phosphoric compounds . The invention also relates in part to an improved hydroformylation process for making one or more aldehydes, which includes (i) in at least one reaction zone, a metal-organic phosphite coordination dislocation catalyst and optionally Reacting one or more olefinically unsaturated compounds with carbon monoxide and hydrogen in the presence of a selected free-state organic phosphite ligand to produce a reaction product fluid containing one or more aldehydes, and (ii) in at least one separation zone In the zone or in the at least one reaction zone zone, one or more acids are separated from the reaction product fluid. Improvements include preventing and / or reducing the hydrolytic degradation of any of the organic phosphite ligands and the metal-organic Deactivation of phosphite coordination catalysts by introducing at least one amount of phosphoric acid sufficient to remove at least one amount of phosphoric acid from the reaction product fluid in the at least one reaction zone and / or the at least one separation zone Water of a chemical compound, treating at least a portion of the reaction product fluid derived from the hydroformylation process and also containing phosphoric compounds formed during the hydroformylation process, and (b) at least In an acid removal zone, at least a portion of the water containing the phosphoric acid compound removed from the reaction product fluid is used with one or more acid removal substances sufficient to remove at least some amount of the phosphoric acid compound from the water. deal with. A further part of the present invention relates to an improved hydroformylation method for producing aldehydes, which comprises (i) in at least one reaction zone, a metal-organic trans-acid vinegar coordination dislocation catalyst and optional use 'Reacting one or more olefinically unsaturated compounds with carbon monoxide and hydrogen' in the presence of a free-state organic phosphite ligand to produce a reaction product fluid comprising one or more aldehydes, and (ii) in at least one separation zone Or in the at least one reaction zone, since _ _ · 20- This paper size is applicable to Chinaϊϋ (公 巧-~ ----------------- IT ----- -φ (Please read the precautions on the back before filling this page) 509694 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (18) The reaction product fluid separated one or more aldehydes, and its improvement matters Including preventing and / or reducing the hydrolytic degradation of any of the organic phosphite ligands, and the inactivation of the metal-organophosphite coordination catalyst, in a manner such that it is removed from the at least one reaction zone or The at least one separation zone, at least a part of which is derived from The hydroformylation process and also a reaction product fluid containing an acidic compound formed during the hydroformylation process, in at least one scrubbing zone, using at least a sufficient amount of phosphoric acid to remove from the reaction product fluid Compound water, treating at least a portion of the reaction product fluid derived from the benzylation method and also having a phosphoric acid compound formed during the hydroformylation method, (C) rendering the treated reaction product The fluid returns to the at least one reaction zone or the at least one separation zone. In at least one scrubbing zone, at least a portion of the water containing the phosphoric acid compound removed from the reaction product fluid is used. The water removes at least some amount of one or more acid-removing substances of a phosphoric acid compound, and optionally replaces the one or more acid-removing substances. BRIEF DESCRIPTION OF THE DRAWINGS FIG. Simplified flowchart of a method for removing one or more amidines for recovery and return to the hydroformylation process. / General method The method of the present invention may be asymmetric or asymmetric The preferred method is asymmetrical and can be performed in any continuous or semi-continuous manner, and involves any desired catalyst liquid and / or gas recycling operation. Specific methods for producing products from—or multiple reactants, and Reaction conditions for this method --------.-- install ------ order ------ (Please read the precautions on the back before filling this page) -21-509694 Central Standard of the Ministry of Economic Affairs A7 printed by the Bureau ’s Consumer Cooperatives ----- --- B7 V. (19) A ~ --__ and ingredients are not important features of the present invention. The processing technology of the present invention may be equivalent to the conventional methods used so far. Any known processing technology used. For example, 'This method can be performed in a liquid or gas state and in a continuous, semi-continuous or batch manner, and involves liquid recycling and / or gas recycling operations, or such systems Combination, as needed. Similarly, the manner or order of adding reaction components, catalysts and solvents is not important and can be achieved in any conventional manner. As used herein, the term "reaction product fluid" is intended to include, but is not limited to, a reaction mixture containing a certain amount of any one or more of the following: a metal-organophosphite complexation catalyst ⑼, free-state organic phosphite ligand, (C) one or more phosphoric compounds formed in the reaction, (d) products formed in the reaction, (e) unreacted reactants' and (f) An organic solubilizer for the metal-organic phosphite g coordination complex catalyst and the free-state organic phosphite ligand. This reaction product stream system covers, but is not limited to, reactions in the reaction zone Medium, (b) the flow of reaction medium on the way to the separation zone, (C) the reaction medium in the separation zone, (d) the circulating liquid flow between the separation zone and the reaction zone, from the reaction zone Take out the reaction medium for water treatment using the belt or separation zone, (f) the reaction medium after taking out and use water treatment, (g) the reaction medium after returning to the reaction zone or separation zone after treatment, and (h) Reaction medium in an external cooler. Includes conventional conventional synthesis using a metal-organic transesterate coordination catalyst in a conventional manner, which will contain a reaction product fluid containing a phosphate compound derived from the process and also containing the phosphoric acid compound formed during the process Metal-organic phosphite coordination catalyst, use water sufficient to neutralize and remove at least some amount of the one or more phosphoric compounds, _ -22- This paper applies Chinese national standard (CNS) A4 specifications (210 X 297 mm) (please read the notes on the back before filling out this page) 4 items. Fill in.-Order printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Printed A7 __-_____ B7 V. Invention Explanation (20.1 ~ ^ ~ '—— Treat the reaction product fluid, and (b) use water that contains phosphoric acid compounds removed from the reaction product fluid, and use enough to remove at least some amount of the one or Treatment of acid-removing substances of various phosphoric compounds to prevent and = or reduce the hydrolytic degradation of organic phosphite ligands and the inactivation of metal-organic phosphatidyl complex coordination catalysts ο These methods Illustrative example, package For example, hydroformylation, hydrogenation (intramolecular and intermolecular), hydrocyanation, hydrofluoridation, hydroesterification, amination, alcoholysis, carbonylation, hydrazone isomerization Effect, transfer hydrogenation, etc. The preferred method involves the coordination of organic compounds with carbon monoxide, or with carbon monoxide and a third reactant, such as hydrogen, or with hydrogen cyanide, in a catalytic amount of metal_organic phosphite. The reaction is in the presence of a catalyst. The best methods include argon methylation, hydrocyanation, and carbonylation. Murine methylation can be performed according to conventional procedures known in the art. For example, acids can be obtained by converting olefin compounds Carbon monoxide and hydrogen are produced by reaction under the conditions of hydrogen methylation in the presence of a metal-organophosphite coordination dislocation catalyst as described herein. Alternatively, amino acids can be prepared by reacting epoxy compounds, carbon monoxide, and hydrogen in the presence of metal formazan in the presence of a metal-organic phosphite coordination dislocation catalyst as described herein. Acetal can be hydrogenated to diol, for example, hydroxypropanal can be hydrogenated to propylene glycol. The hydroformylation process is described more fully below. Intramolecular hydrogenation can be performed according to conventional procedures known in the art. For example, the removed aldehydes containing 3 to 7 carbon fluorene groups can be converted under the conditions of hydrogenation in the presence of the metal-organic phosphite coordination catalyst described herein. Into cyclic ketones. ________-23-The paper size is suitable for financial and family care standards (CNS) A4 size qx297 mm) -------------- Siyi ^ Please read the precautions on the back before filling this page) -Order_ 509694 A7 B7 Printed by the Consumer Cooperative of the Central Accreditation Bureau of the Ministry of Economic Affairs 5. Description of the invention (21 Intermolecular hydrogenation can be performed according to customary procedures known in the art. For example, ketones can be obtained by converting fluorene It is prepared by reacting with aldehyde under the conditions of hydrogenation in the presence of the metal-organophosphite complexing catalyst described herein. Hydrocyanation can be performed according to conventional procedures known in the art. For example, a nitrile compound can be prepared by reacting an olefin compound with hydrogen cyanide under the conditions of hydrocyanation in the presence of a metal-organophosphite coordination dislocation catalyst described herein. Preferred hydrogen The cyanation method involves making a non-conjugated acyclic aliphatic monoolefin, a monoolefin conjugated to an ester group, such as methyl pentamate, or a monoolefin conjugated to a nitrile group, such as 3_ Pentenonitrile, with hydrogen cyanide source, contains zero-valent nickel and bidentate chelated phosphite The catalyst precursor composition of the ligand reacts in the presence of a terminal organic nitrile, such as adiponitrile '5-cyanovalerate or 3- (perfluoroalkyl) propionitrile. This reaction is preferably It is carried out in the presence of a Lewis acid accelerator. Illustrative examples of the hydrocyanation method are disclosed in US Pat. Nos. 5,523,453 and WO 95/14659, the disclosures of which are hereby incorporated by reference. Hydrogenation can be based on this Conventional procedures known in the art are performed. For example, amidoamines can be coordinated by the metalorganophosphites described herein under the conditions of hydrogenation of olefins, carbon monoxide and primary or secondary amines or ammonia. Hydrogenation can be performed according to conventional procedures known in the art. For example, esters can be prepared by reacting olefins, carbon monoxide, and alcohols under the conditions of hydroesterification. The metal-organophosphite complex catalyst is reacted in the presence of the catalyst. -24- This paper size is applicable to China National Standard (CNS) A4 specification (B0X297 mm)

509694 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (22) Amination can be performed according to customary procedures known in the art. For example, amines can be prepared by reacting an olefin with a primary or secondary amine in the presence of a metal-organophosphite coordination dislocation catalyst as described herein under ammonolysis conditions. ... alcoholysis can be performed according to conventional procedures known in the art. For example, ethers can be prepared by reacting an olefin with an alcohol under the conditions of alcoholysis in the presence of a metal-organophosphite coordination dislocation catalyst as described herein. Peeping can be performed according to conventional procedures known in the art. For example, lactones can be prepared by treating allyl alcohols with carbon monoxide in the presence of a metal-organophosphite coordination dislocation catalyst as described herein under carbonylation conditions. Isomerization can be performed according to conventional procedures known in the art. For example, propyl alcohol can be isomerized under isomerization conditions in the presence of the metal-organophosphite coordination catalyst described herein to produce acids. Diversion hydrogenation can be performed according to conventional procedures known in the art. For example, alcohols can be prepared by reacting a ketone with an alcohol under the conditions of transfer hydrogenation in the presence of a metal beta organic phosphite coordination catalyst as described herein. The permissible starting materials covered by the method of the present invention are, of course, selected according to the specific methods of the two desired rows. This kind of starting material is known in the art. It can be used according to customary methods. Examples of the modification of the starting reaction substance include, for example, substituted and unsubstituted aldehydes (intramolecular hydrogen hydration), associating hydrocarbons (methylformation, carbonylation, intermolecular hydrogen). ^ ------ IT ------ (Please read the notes on the back before filling this page)

Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs / U At-m ^ Hydrocyanation, Hydrogenation, Hydroesterification, Amination, Alcolysis), Ketones (Transfer Hydrogenation), Epoxy Compounds (hydromethylation, cyanide), alcohols (carbonylation) and their analogs. Illustrative examples of suitable reactants for achieving the method of invention 2 are detailed in the Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, 1996, the relevant parts of which are incorporated herein by reference. Illustrative examples of metal-organophosphite complex catalysts that can be used in the methods covered by the present invention, as well as their preparation methods, are known in the art, and include the patents indicated below Revealed in. Normally. Such catalysts may be preformed or formed on the spot 'as described in these references and essentially comprise a metal in a mismatched combination with an organic phosphite ligand. These active species may also contain carbon oxide and / or hydrogen which is directly bound to the metal. Catalysts that can be used in these methods, including metal-organophosphite coordination catalysts, can be optically active or non-optically active. Permissible metals constituting metal-organophosphite complexes, including Groups 8, 9 and 10 metals, selected from germanium (Rh), cobalt (Co), iridium osmium, ruthenium (Ru), iron (Fe ), Nickel (Ni), palladium (Pd), platinum (Pt), iron (Os) and mixtures thereof, among which the preferred metals are germanium, cobalt, iridium and ruthenium, more preferably germanium, cobalt and ruthenium, especially germanium . Other permissible metals include Group 11 metals selected from copper (CU), silver (Ag), gold (Au) and mixtures thereof, and group 6 metals selected from chromium (〇 ·), molybdenum (Mo), tungsten (W) and mixtures thereof. Mixtures of metals from Groups 6, 8, 9, 10 and 11 can also be used in the present invention. Permissible organic phosphites that constitute metal-organic phosphite coordination complexes and free-state organic phosphite ligands-26- This paper size applies to China National Standard (CNS) A4 (210X297 mm) —------—------ Order ----- (Please read the notes on the back before filling out this page) A7 B7 V. Description of the invention (24 t-body, including entering the bill-2) -, Tri- and higher polyorganophosphites. If desired, a mixture of such ligands can be used in metal-organophosphite coordination catalysts and / or free state ligands, and Such mixtures may be the same or different. The present invention is not intended to be limited in any way by such permissible organic phosphite ligands or mixtures thereof. It should be noted that the successful implementation of the present invention is not dependent on And it is not based on the exact structure of the metal-organophosphite complex, which can exist in its mononuclear, dinuclear and / or more shuttle-like form. In fact, the exact structure is unknown. Although not intended here Bound by any theoretical or mechanical discourse, but these catalyst species should be used It seems to be in its simplest form, which basically contains a metal in a mismatched combination with an organophosphite ligand and carbon monoxide and / or hydrogen. The Consumers' Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs is printed here and is in the scope of patent applications The "complex" used in the term, means that one or more molecules or primitives rich in electrons that can exist independently are depleted with one or more electrons that can also exist independently. Coordination compound formed by the combination of molecules or atoms. For example, organic phosphorous plate ester ligands that can be used in or in can have one or more fluorene donor atoms, each with a pair that can be used or not shared Each of the electron pairs can independently form a covalent bond in coordination with the metal (eg, via chelation). A rolled carbon (which is also appropriately classified as a ligand) can also exist and be mismatched with the metal 2. The final composition of the complex catalyst may also contain other coordinations *, such as the chloride ^ anion, to satisfy the coordination position or the nuclear charge of the metal. The condition of other coordination groups =, 'including, for example, dentin (C1, Br , J), fluorenyl, aromatic , Substituted acyl, CF3, C2F5, CN, (R) 2PO and RP (square) (〇u) square (wherein

This paper size applies to China ^^^^ 2WX297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 509694 A7 _____B7 —___ V. Description of the invention (25) Each R is the same or different, and it is replaced or not Substituted hydrocarbon groups, such as fe or aryl), acetate, ethylpyruvate, so4, pf4, PF6, no2, no3, ch30, ch2 = chch2, CH3CH = CHCH2, c6h5cn, CH3CN, NH3, pyridine, (C2H5) 3N, mono-, di-, and tri-olefins, tetrahydrofuran, etc. Of course, it should be understood that these better complexes do not contain any other organic ligands or anions that may poison the catalyst or have an adverse effect on the performance of the catalyst. In methods catalyzed by metal-organic transesterate coordination complexes, such as hydromethylation, the active catalyst is preferably free of elements and sulfur that are directly bound to the metal, but it is not absolutely necessary. The number of coordination positions that can be used on such metals is known in the art. Therefore, the catalyst species may include a hybrid catalyst mixture in its monomeric, dimeric, or higher nuclear form. It is preferably characterized in that each metal, such as germanium, contains at least one organic phosphorous acid in the molecular complex. The purpose of the molecule. For example, in view of the carbon monoxide and hydrogen used in the hydroformylation reaction, the catalyst species recognized as the better catalyst used in the hydroformylation reaction, in addition to the organic phosphite ligands, can be used with Carbon monoxide and hydrogen are mismatched. The organic phosphite which can be used as the metal-organic arsenite Q complex coordination catalyst and / or the free-state ligand of the method and the reaction product fluid of the present invention can be non-palladium ( Optically inactive) or palmar (optically active) versions' are well known in the art. By "free-state ligand" is meant that the ligand is not complexed (bonded or bonded to a metal) with a metal, such as a metal atom of a mismatched catalyst. As pointed out in this article, the present invention < Wanfa, and especially the hydroformylation method, can be adapted to the free-state organic phosphorous acid I _____ 28- This paper is of suitable size; (CNS) A4 size (21〇x297 ^^ ---. Binding (please read the notes on the back before filling in this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A 7 B7 V. Description of the invention Strictly know the presence of the ligand. Non It is better for palmitic organic phosphite system. It can be used as a ligand for the metal-organic phosphite coordination dislocation catalyst containing the reaction product fluid of the present invention, and / Or it can be any free-state organic phosphite coordination compound in the reaction product fluid, which is a monoorganic phosphite, a diorganophosphite, a triorganophosphite, and an organic polyphosphite compound. . Such organic phosphite ligands that can be used in the present invention and / or its preparation method are known in the art. $ Representative monoorganic phosphites can include those with the following formula : R1—〇 一 p \ 〇 / (I) where R1 represents containing 4 to 40 carbon atoms Or more substituted or unsubstituted trivalent hydrocarbon groups, such as trivalent acyclic and trivalent cyclic groups, such as trivalent hypocarbyl groups, such as those derived from 1,2 > trimethylolpropane, And its analogs, or trivalent cycloalkyl groups, such as those derived from trihydroxycyclohexane, and the like. Such monoorganophosphites can be found in more detail, for example, in U.S. Patent 4,567,306, which discloses The content is for reference in this document. 〇 Representative two organic phosphites, which can include the following formula: -29- This paper size is applicable to the Chinese National Standard (CNS) M specifications (210X297 mm) (Please read the back (Please fill in this page again)

509694 A7 B7 V. Description of the invention (27)

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs where R2 represents a substituted or unsubstituted divalent hydrocarbon group containing 4 to 40 carbon atoms or more, and W represents a process containing 1 to 18 carbon atoms or more A substituted or unsubstituted monovalent hydrocarbon group. Representative substituted and unsubstituted monovalent hydrocarbon groups represented by W in the formula (I) above, including alkyl and aryl groups, and representative substituted and unsubstituted divalent hydrocarbon groups represented by r2, including two Valence acyclic group and divalent aromatic group. Illustrative examples of divalent acyclic groups include, for example, sulfenyl, sulfenyl-oxy- sulfinyl, sulfinyl-NR4- sulfinyl, where R4 is hydrogen or substituted or unsubstituted Monovalent hydrocarbon groups, for example, alkyl groups having 1 to 4 carbon atoms; alkylene alkylene groups, cycloalkylene groups, and the like. More preferred divalent non-cyclic groups are divalent secondary alkyl groups, such as those more fully disclosed in U.S. Patents 3,415,906 and 4,567,302, the disclosures of which are incorporated herein by reference. Illustrative examples of divalent aromatic groups include, for example, subaryl, subbisaryl, subaryl-subalkyl, subaryl-subalkyl-subaryl, subaryl-oxy-subaryl And aryl-NR4-subaryl, in which R4 is as defined above, s-aryl-S- aryl, and s-aryl-S-alkylene. Preferably, R2 is a divalent aromatic group, such as those more fully disclosed in U.S. Patents 4,599,206, 4,717,775, 4,835,299, etc., the disclosure of which is incorporated herein by reference. A representative example of a better type of diorganophosphite is the one with the following formula: -30- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) Page) 509694 Α7 Β7 V. Description of the invention (28

p ~ ow (III) where w is as defined above, and each & is the same or different ▲? —Small π., or unsubstituted aryl, each y is the same or different, and is 0 or】 Number 値, Q represents a divalent bridging group, selected from _C (R3) ^, _〇_, each, __4-, Si (R5) 2-, and each R3 is the same or different, and represents Hydrogen, I alkyl, phenyl, tolyl, and p-methoxyphenyl having 1 to 12 carbon atoms, R4 is as defined above, each R5 is the same or different, and represents hydrogen or methyl, and m is 0 or Number of 1 値. Such diorganophosphites are described in more detail in, for example, U.S. Patents 4,599,206, 4,717,775 and 4,835,299, the disclosures of which are incorporated herein by reference. / The representative three organic imidates can include those with the following formula: and said to be replaced (please read the notes on the back first and fill out the bonbon)-loaded ·, 1r Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs / OR6 R ^ ~ OR6 〇R6 < IV) wherein each R6 is the same or different and is a substituted or unsubstituted monovalent hydrocarbon group, such as alkyl, cycloalkyl, aryl, alkaryl, and aralkyl, It may contain 1 to 24 carbon atoms. Illustrative examples of triorganophosphites include, for example, trialkylphosphite, dialkylarylphosphite, alkyldiarylphosphite, triarylphosphite, and the like, such as phosphorous acid Trimethyl ester, -31 This paper is applicable to medium specifications (袭) .—........-—-....... —I — 509694 Α7 Β7 29 5. Description of the invention Triethyl phosphite Ester, butyl diethyl phosphite, tri-n-propyl phosphite, tri-n-butyl phosphite, tri-n-ethylhexyl phosphite, tri-n-octyl phosphite , Tri-n-dodecyl phosphite, dimethylphenyl phosphite, diethylphenyl phosphite, methyldiphenyl phosphite, ethyldiphenyl phosphite, phosphorous acid Triphenyl ester, trisylphosphite, bis (3,6,8 ~ di-second-butyl-2-fluorenyl) methyl vinegar, bis (3,6,8_ Tri-tertiary-butyl_2 · fluorenyl) cyclohexyl ester, tri-tertiary-tertiary-butyl-2-fluorenyl) phosphite, bis (3,6,8_tri-tertiary- Butyl winter fluorenyl) (4-biphenyl) ester, phosphorous & L bis (3,6,8-bis-third-butyl_2-fluorenyl) benzene Ester, bis (3,6,8-bis-second-butyl-2-¾: :) bis (3,6,8-di-second-butyl-2-¾: yl) ester, bis (6,8-) Di-second-butyl-2-fluorenyl) (4-; nullinophenyl) esters and their analogs. The most preferred triorganophosphite is triphenyl phosphite. Such triorganophosphites are described in more detail in, for example, U.S. Patents 3,527,809 and 5,277,532, the disclosures of which are incorporated herein by reference. The representative organic polyphosphonolide contains two or more tertiary (trivalent) phosphorus atoms, and can include those with the following formula: (Please read the precautions on the back before filling this page)

, 1T R: Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, Cr, P— < a P-0- X b (V) where X represents a substituted or unsubstituted carbon atom containing 2 to 40 carbon atoms Substituted n-valent organic bridging groups, each R7 is the same or different, and represents a divalent organic group containing 4 to Qi carbon atoms, each R8 is the same or different, and represents containing

210 × 2 () 7 mm) • i— 8— · ----- 1- I ....... I I --- two 509694 A7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ^^ _ B7 V. Description of the invention (30) A substituted or unsubstituted monovalent hydrocarbon group of 1 to 24 complete atoms, a and b may be the same or different, and each has a number of 0 to 6, and the condition is a + The sum of b is 2 to 6, and η is equal to a + b. Of course, it should be understood that when a has a number of 2 or more, each R7 group may be the same or different. For any particular compound, each R8 group can also be the same or different. The representative η-valent (preferably divalent) organic bridging group represented by X above, and the representative divalent organic group represented by R7, include both acyclic groups and aromatic groups. , Such as alkylene, alkylene-Qm-alkylene, cycloalkylene, aryl, bis-biaryl, aryl-alkylene, and aryl- (CH2) y-Qm- ( CH2) y-subaryl, etc., wherein each Q, y and m are as defined above in formula (m). The non-cyclic group represented by X and R7 in the above is more preferably a divalent hypoalkynyl group, and the aromatic group represented by X and in the above is more preferably a divalent subaryl group and a bisbis group. Aryl, for example, is disclosed more fully in, for example, U.S. Patents 4,769,498; 4,774,361: 4,885,401; 5,179,055; 5,113,022; 5,202,297; 5,235,113; 5,264,616 and 5,364,950; and European Patent Application Publications 662,468, among others. The disclosure is incorporated herein by reference. Representative preferred monovalent hydrocarbon groups represented by each R8 group hereinabove include alkyl and aromatic groups. Examples of preferred organic polyphosphites can include bisphosphites, such as those with the following formulas (VI) to (vm): (Please read the precautions on the back before filling this page): p—ο-χ 2 (VI) -33- This paper size applies to Chinese National Standard (CNS) A4 (210X29? Mm) 509694 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (31 rL〇, fP—〇 〆: ρ-ο- X 2, 〇, cr (VII), 〇— Ό—R8 (VIII) wherein each of R7, R8 and X of the formulae (vi) to (vm) is the same as defined above with respect to formula ⑺ Same. Each of R7 and X preferably represents a divalent hydrocarbon group, selected from the group consisting of hypoxyl, subaryl, subaryl-alkylidene-subaryl, and hypobiaryl, and each R8 group represents a monovalent hydrocarbon group. Is selected from the group consisting of alkyl and aryl. Such organic phosphite ligands of the formulae (V) to (_) can be found in, for example, U.S. Patents 4,668,651; 4,748,261; 4,769,498; 4,774,361; 4,885,401; 5,113,022; 5 5,179,055; 5,202,297; 5,235,113; 5? 254? 741; 5,264,616; 5,312,996; 5,364,950; and 5,391,801. And in the present text by reference. More preferably the bis-type organophosphate representative example, to have the following formula based (K) to ρα) by

(DO (please read the precautions on the reverse side and fill in this page again) Revision 4. Applicable to the standard country and the country A. Rule paper on paper 17 509694 kl B7 V. Description of the invention (32 r— (? H2) -〇 y

(CH2) y Ar-O 〇—r8 Ό—R8 (X)

Ar——O (CH2) y Qm (CH2) y Ar——〇P—O ~ X — Ό, cr ί Please read the notes on the back before filling in this page, > (XI) Staff of Central Bureau of Standards, Ministry of Economic Affairs Consumption cooperatives print where Ar, Q, R7, R8, X, m & y are as defined above. The patriline represents a divalent aryl- (CH2) factory (Q) m_ (CH2) factory aryl group, where each y individually has a 値 of 0 or 1; m has 0 or! Where Q is Q, and C (R3) 2 'wherein each R3 is the same or different and represents hydrogen or methyl. Each alkyl group of the R8 group defined in the above 3, may preferably contain 1 to 24 carbon atoms, and the groups 々, X, R7 and R8 defined above in the formulae (EX) to (XI) above. Each aryl group 'may contain 6 to 18 complete atoms, and the groups may be the same or different, and a preferred alkylene group of X may contain 2 to 18 carbon atoms, and a preferred group of R7; Contains 5 to 18 carbon atoms. In addition, the divalent octyl group of the above formulae and the divalent aryl group of X are preferably phenylene groups, and the bridging group represented by the (ch2) y_ (Q) m (0¾) plant is Combined with the phenylene group, its position is ortho to the oxygen atoms of the formulas, and the phenylene group is best connected to the phosphorus atoms of the formulas, and the scale can be appropriately adjusted, I ... 1— ml · V. Description of the invention (33) Α7 Β7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. When any substituent is present on such a phenylene group, it should preferably also be bonded to the para and / or ortho position of the phenylene group which is related to the bonding of a particular substituted phenylene group to the oxygen atom of its phosphorus atom. on. Of course, any of the Rl, R, R6, R7, R8, w, x, Q and ^ groups of such organic phosphites of formulae (I) to (XI) above may not be inappropriate if necessary It also adversely affects any desired substituent substitution containing i to 30 carbon atoms which is the desired result of the method of the present invention. The substituents' that may be on this group are, of course, in addition to the corresponding hydrocarbon groups such as alkyl, arylaralkyl, alkaryl and cyclohexyl substituents, and may include, for example, silane groups such as Si (R10) 3 ; Amine group, such as -N (R10) 2; Phosphine group, such as _aryl-P (R10) 2; Amidino group, such as _C (0) Ri0, Amino group, such as _〇C (〇) Rio Fluorenylamino, such as _〇}] $ 1110) 2 and -n (r1 ()) cor1 () ·, sulfofluorenyl, such as -S〇2R1〇, alkoxy 'such as -OR10; For example, -SOR10, a secondary acid group, such as SR10, a phosphonic acid group, such as _p (〇) (r1〇) 2, and a prime, nitro, cyano, trifluoromethyl, hydroxyl, etc., each of which is R10 Groups individually represent the same or different monovalent hydrocarbon groups having 1 to 18 carbon atoms (such as alkyl, aryl, aralkyl, alkaryl, and cyclohexyl), with the proviso that an amine substituent such as _ N ( In R; G) 2, each rM is used to represent a bivalent bridging group that can also form a heterocyclic group having a nitrogen atom, and in a sulfonylamino substituent such as 0) 2 and -N (R1G) COR10, Each R10 bonded to N may also be hydrogen. It should be understood, of course, that any substituted or unsubstituted hydrocarbyl groups that make up a particular organic transester may be the same or different. More specifically, examples of substituents include primary, secondary, and tertiary alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, butyl, and second-butyl. -36 -__ Paper size applies Chinese National Standard (CNS) A4 specification (21〇 × 297 mm) " {Please read the precautions on the back before filling out this page} One Pei • • Order _ Ministry of Economic Affairs, Central Bureau of Standards, Staff Consumer Cooperation 衽Printed 509694 Α7 B7 V. Description of the Invention (34) group, third-butyl, neo-pentyl, n-hexyl, pentyl, second-pentyl, third-pentyl, iso-octyl, decyl Fluorene, octadecyl and similar groups; aryl groups such as phenyl, fluorenyl and the like; aralkyl groups such as benzyl, phenethyl, trityl and the like; alkylaryl groups, For example, tolyl, xylyl, and the like; cycloaliphatic groups, such as cyclopentyl, cyclohexyl, 1-methylcyclohexyl, cyclooctyl, cyclohexylethyl, and the like; alkoxy, For example, methoxy, ethoxy, propoxy, tertiary-butoxy, -OCH2CH2OCH3, -0 (CH2CH2) 20CH3, _0 (CH2CH2) 30CH3 and the like; aryloxy, such as Phenoxy and its analogs; and sintered groups such as -Si (CH3) 3, -Si (OCH3) 3, -Si (C3H7) 3 and their analogs; amine groups such as _NH2, -N ( CH3) 2, _NHCH3, _NH (C2H5) and their analogs; arylphosphine. Groups, such as _P (C6H5) 2 and their analogs; fluorenyl groups, such as -C (0) CH3, -c (o) c2h5, -c (o) c6h5 and their analogs; carbonyloxy, such as -c (o) och3 and its analogs; oxycarbonyl, such as -o (co) c6h5 and its analogs; amido, such as- CONH2, -CON (CH3) 2, -nhc (o) ch3 and their analogs; sulfofluorenyl, such as -S (0) 2C2H5 and its analogs; sulfinylfluorene, such as -S (0) CH3 and its Analogs; sulfinate groups, such as -SCH3, -SC2H5, -sc6h5 and their analogs; phosphonic acid groups, such as -p (o) (c6h5) 2, -p (o) (ch3) 2, -P ( 0) (C2H5) 2, -P (0) (C3H7) 2, j (0) (C4H9) 2, -P (0) (C6H13) 2, -P (0) CH3 (C6H5), -P (〇 XH) (C6H5) and its analogs. Specific examples of such organic phosphite ligands include the following: Phosphite: fe 2-di-di-butyl-4-methyllactyl (3,31-di-second-butyl-5 , 5f-dimethoxy-1, Γ_biphenyl-2, diyl) ester, which has the following formula: This paper size applies to China National Standard (CNS) Α4 specification (210 X 297 mm) (please first Read the notes on the back and fill out this page), 1Τ #. 509694 A7 B7 V. Description of the invention (35)

Ligand A methyl phosphite (3,3, -di-third-butyl-5,5, -dimethoxy-UL biphenyl-2,2'-diyl) ester, which has the following Formula: (Please read the precautions on the back before filling this page)

Ligand B Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs [6,6,-[[4,4, -bis (1,1-dimethylethyl)-[1,1'_linkedyl]- 2,2'-monoyl] bis (oxy)] bis-diphenylphosphonium [d, f] [l, 3,2] -dioxophosphate heptamidine, which has the formula:

509694 A7 B7 V. Description of the invention (36) 6,6 '_ [[3,3 · -bis (1,1-dimethylethyl) -5,5 · -dimethoxy- [1,1' _Biphenyl] -2,2 · _yl] bis (oxy)] bis-dibenzo [ming [1,3,2] dioxophosphate heptamidine, which has the formula: 〇ChU OCH〇

Ligand D 6,64 [3,3,, 5,5, -Di (151-dimethylpropyl)-[1,1 biphenyl] -2,2 didiyl] bis (oxy )] Bis-dibenzo [4 £ 1 [1,3,2] dioxophosphate heptamidine, which has the formula: 3, CK CH, 丨 3

(Please read the precautions on the back before filling out this page); Binding and ordering Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

Ligand E 6, heart [[3,3 ', 5,5,-[(1,1-dimethylethylbiphenyl] fluorenediyl] bis (oxy)] bis-dibenzo [ d, f] [l, 3,2] -dioxophosphonium heptamidine, which has the following formula: -39- This, our scale is applicable to the Chinese National Standard (CNS) A4 specification (2iOX 297 mm) 509694 A7 B7 V. Description of the invention (37)

Ligand F diphosphite (2R, 4R) -di [di / "meaning ^ brother-third-pentyl ^ '-biphenyl)]'. Amyl ester, which has the formula: (please first Read the notes on the back and fill out this page) CH% / CH (

‘CH 丨 3

CH

CH

C (CH3) 2C2H5

C2H5 (CH3) 2C C (CH3) 2C2H5 C2H5 (CH3) 2C C2H5 (C 1- ^ 3) 2 ^

C2H5 (CH3) 2C C (CH3) 2C2H5 C (CH3) 2C2H5 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs

Ligand G diphosphite (2R, 4R) -di-P, 2Η3,3 ', 5,5 · _. • Third, butyl ^ biphenylphenyl 2,4-pentyl ester, which has the following Formula: -4ΓΚ This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) CHa, CH,

(CH3) 3C

(CH3) 3C

C (CH3) 3 C (CH3) 3 C (CH3) 3 509694 A7 B7 V. Description of the invention (38), CH〇 2. r

CH CH c (ch ^ 3 ο OP (ch3) 3 O-P R-0 ligand H * diphosphite (2R, 4R) J [2,2,-(3,3, -di-pentyl- 5,5f-dimethoxy-U'-biphenyl)]-2,4-fluorenyl ester, which has the following formula: (Please read the precautions on the back before filling this page)

⑶ gas / CH2 / ⑶3 • CH C (CH3) 2C2H5 ㈣, r〇i Ρ °° C2H5 (CH3) 2p 〇 〇

och3 -C (CH3) 2C2Hc ch3〇 C2H5 (CH3) 2C och3

Ligand I Diphosphite (2R, 4R) -di [2 /-(3 / -di-third-butyl-5,5 * -dimethyl-1] printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs , 1 · -biphenyl)]-2,4-pentyl vinegar 'which has the following formula

‘·· CH, 〇H

This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) 509694 A7 B7 V. Description of invention (39)

Ligand J diphosphite (2R, 4R) -bis [2,2,-(3,3, -bis-third-butyl-5,5, -diethoxy-1,1'-linked Phenyl)]-2,4-pentyl ester, which has the following formula: ch3ch2o- X / CH ^^ cn CH 3 C (CH3) 3 0? C (CH3) 3 P "〇, s \ och2ch3 \ CH3CH2〇 c (CH3) 3 〇ch2ch3 ligand κ diphosphite (2R, 4R) -di [2,2,-(3,3, -di-third-butyl-5,5f-diethyl-l , R-biphenyl)]-2,4-pentyl ester, which has the following formula: ⑶ '/ CH2, strict

CH '" CH (Please read the notes on the back before filling this page)

C (CHb) 3 O C (CF ^ 3

ch2ch3 ch2ch3 Printed by the Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs

Ligand L diphosphite (2R, 4R) -bis [2,2,-(3,3 · -bis-third-butyl-dimethoxy-l, r-biphenyl)]-2, 4-pentyl S purpose 'which has the following formula: This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ΑΊ Β7 V. Description of the invention (40)

⑶ '/ Ch2' strict QH, QH

Ligand M 6-[[2-[(4,6-bis (1,1-dimethylethyl) -1,3,2-phenylphosphonium dioxo-2-yl) oxy] _3, 3, -bis (1,1-dimethylethyl) -5,5, -dimethoxy [1, Γ_biphenyl] -2_yl] oxy] _4,8-bis (1, 1-monomethylethyl) -2,10-monomethoxydiphenylhydrazone [d, p- [I, 3,2] dioxophosphate heptamidine, which has the following formula:

(Please read the notes on the back before filling this page)

, 1T Printed ligand N 6-[[241,3,2-phenylphosphonium dioxo_2_yl) oxy] _3,3L bis (1,1_dimethylformaldehyde) printed by the consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Ethyl) -5 5, _ monomethoxy [l, r-biphenyl] -2 · yl] oxy] -4,8-bis (1,1-dimethylethyl) _2,1〇 -Dimethoxydiphenylhydrazone [d, fj [i, 3,2] dioxophosphate heptamidine, which has the formula:

--------- _-43-The paper ruler H 509694 A7 B7 V. Description of the invention (41

Ligand 06-[[2f-[(5,5-dimethyl-1,3,2-dioxophane-2-yl) oxy] -3,3'-bis (1,1- Dimethylethyl) -5,5'-dimethoxy [1,1L biphenylyl] oxy] -4,8-bis (1,1-dimethylethyl) -2,10- Dimethoxydibenzo [4magic [1,3,2] dioxophosphate heptafluorene, which has the following formula:

(Please read the notes on the back before filling this page) 〇 ~ * ch2, c, ch3

Ligand P Phosphorous acid 2,-[[4,8-bis (1,1-dimethylethyl > 2,10-dimethoxydiphenylhydrazone [Ming [1,3,2]- Dioxophosphate heptamyl groups] oxy] -3,3, -bis (1,1-dimethylethyl) -5,51-two paper sizes are applicable to China National Standard (CNS) A4 specifications (210X297) (Centi) 509694 ΑΊ B7 V. Description of the Invention (42) Methoxy [1, Γ-biphenyl] -2-ylbis (4-hexylphenyl) vinegar, which has the following formula: och3 och3

c (ch3) 3 〇 ^^ (Ch2) 5ch3 〇 ^^ MCH2) 5CH3 (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs

Ligand Q 2 _ [[2-[[4,8, -bis (1,1-dimethylethyl), 2,10-dimethoxydiphenylhydrazone- [〇1,1] [1,3,2] Dioxetazone-6-yl] oxy] _3- (1,1-dimethylethyl) -5-methoxyfluorenyl] fluorenyl] -4-methoxy , 6- (1,1-dimethylethyl) phenyldiphenyl ester 'has the following formula: 〇ch3 och3 (〇h3) 3c ^^ 2 " N ^ c (ch3) 3 〇〇

C (CH3) 3 / I P; ^

Ligand R 3-Methoxy-1,3-cyclohexamethylene phosphite [3,6-bis (1,1-dimethylethyl)--45- This paper is for Chinese country Standard (CNS) A4 specification (2ί0X297 mm)

43 / [Speaking clearly, with hair in vertical position,] il-based naphthalene 2-.

(CH3) C

P-〇

〇One P

C (CH3) ligand S 2,5-bis (!, 1-dimethylethyl) -M-phenylenesulfonic acid [2,4_bis (1,1-dimethylethyl) Group) phenyl] ester, which has the formula: C (CH3) 3- 0- p. -〇 ~ O ^ C (CH3) 3 _ c (ch3) 3 C (CH3) 3 2 _ c (ch3) 3 2 (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs

Methylene secondary phenyl [2,4-bis (u_dimethylethyl) phenyl] ester of ligand T arsonic acid, which has the formula:

< > ch ^ < P (ch3) 3ch ^ ~ 〇_ | 〇 〇 1 · P p— -〇— < P ^ c (ch3) 3 • C (CH3) 3 2 c (ch3) 3

Ligand U [1, biphenyl R2, _diylmethylmethyl) benzomethoxyphenyl] g purpose, which has the following formula: -46- This paper size applies to Chinese National Standard ) A4 size (21 OX297 mm) ^ 09694

ch3o 《^-〇— c (ch3) 3

OCHaJ C (CH3) 3 · j2 The ligand V printed by the Consumer Cooperatives of the Central Bureau of Quasi-Economic Bureau of the Ministry of Economic Affairs, as described above, can be used in the present invention for the metal-organic phosphite coordination "B catalyst, It is formed by a method known in the art. The metal-organic hypochlorite coordination dislocation catalyst may be in a homogeneous or heterogeneous form. For example, a preformed germanium hydrogenation-carbonyl-organophosphite coordination contact may be prepared. It is also known that it is introduced into the reaction mixture of a specific method. The metal-organic acetic acid coordination catalyst is more preferably derived from a germanium catalyst precursor, which can be introduced into the reaction medium to Active catalysts are formed on the spot. For example, germanium catalyst precursors such as rhodium diacetate pyruvate, (CCOi 2, Rh 6 (COh 6, Rh (N0 3) 3, and the like) can be accompanied by Organic phosphite ligands for the formation of active catalysts on the spot are introduced into the reaction mixture together. In a preferred embodiment of the present invention, germanium dicarbonylacetamidopyruvate is used as the rhodium precursor, and Reacts with organic phosphite ligands in the presence of a solvent to form a catalytic The rhodium-organophosphite complex complex precursor is introduced into the reaction zone along with excess (free-state) organic subscale vinegar ligands for active catalyst formation on the spot. In any case, for the present invention For the purpose, carbon monoxide, hydrogen, and organic phosphite compounds are all ligands that can be mismatched with metals, and the active metal-organophosphite coordination catalyst is used in the hydroformylation reaction. It is enough to exist in the reaction mixture. (Please read the notes on the back before filling this page.) The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X297). 5. Description of the invention (45) More specifically In other words, a catalyst precursor composition can be formed, which basically comprises a soluble metal-organic phosphite coordination complex precursor catalyst, an organic solvent, and a free-form fluorenyl phosphite ligand. This precursor The composition can be made by forming a solution of the wrong starting material, such as germanium oxide, hydride, zinc or salt, such as nitrate, which may or may not be as defined herein The organic phosphite ligands are in a mismatched combination. Any suitable germanium starting material can be used, such as dicarbonylacetamidopropane = rhenium acid, Rh203, Rh4 (CO) 12, Rh6 (c〇) i6, zero 〇3) 3 and organic phosphite ligand germanium carbonyl hydride. If the carbonyl and organic phosphite ligands have not been mismatched with the original germanium, they can be mismatched before or during this procedure. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. It is explained that the preferred catalyst precursor composition of the present invention basically comprises a collapsible germanium carbonyl organic phosphite complex precursor catalyst, a solvent And optionally a free-state organic phosphite ligand, which is made by forming a solution of germanium dicarbonylacetamidopyruvate, an organic solvent, and an organic phosphite ligand as defined herein. The organophosphite ligand can easily replace one of the carbonyl ligands of the precursor of the germanium acetopyruvate complex at room temperature, as evidenced by the release of carbon monoxide gas. If desired, this substitution reaction can be promoted by heating the solution. Any suitable organic solvent may be used in which both the precursor of the dicarbonylacetamidate pyruvate germanium complex and the germanium organic phosphite complex precursor are dissolved. The amounts of germanium complex catalyst precursors, organic solvents and organic phosphite ligands, as well as the preferred embodiments thereof present in such catalyst precursor compositions, obviously can be corresponding to the invention which can be adopted in the present invention. The amount in the method. Experience shows that the ethanoyl radical of this precursor catalyst --------- ~ 48

This paper size is applicable to A4 ^ (2i ^^ FT 509694 A7 --------—__ B7 V. Description of the invention (46) ^ —— η Pyruvate ligand, which is based on this method, for example, methyl hydrogen The tritiation, after it has begun, is replaced by a different ligand such as hydrogen, carbon monoxide or an organic phosphite ligand to form an active complex catalyst as explained above. It does not react under hydrogenation conditions. Acetylacetone containing the precursor catalyst is removed from the reaction medium with the product | and therefore will never be detrimental to the hydroformylation process. | This preferred germanium complex catalyst precursor composition Use is to provide a simple, economical and effective method to deal with the formation of germanium and hydromethane in the precursors of germanium. Startup. Therefore, the metal-organic phosphite compound used in the method of the present invention Position! The mismatch catalyst basically contains a metal that is mismatched with carbon monoxide, which means hydroformylation, and a metal mismatched with an organophosphite ligand. The coordination system is chelated and / or unchelated. Way to combine (mismatch) to metal. Furthermore, " basically contains the term π, which is used in this article At this time, it does not exclude, but in addition to carbon monoxide and organic phosphite vinegar ligands, including hydrogens that are mismatched with metals. Furthermore, this term does not exclude other organic ligands that may also be mismatched with metals. And / or the possibility of anions. Substances that would inappropriately and adversely poison the catalyst or improperly inactivate the catalyst are undesirable 'and therefore the catalyst is most desirably free of contaminants such as metals Combined halogen (printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, such as chlorine and the like), but it is not absolutely necessary. The active metal-organic phosphite coordination catalyst argon and / or carbonyl ligand can be Existence, this is due to the ligand binding to the precursor catalyst and / or due to the formation on the spot, for example, because hydrogen and carbon monoxide gas are used in the hydroformylation method of the present invention. The body can be metal-organic phosphite-49- This paper size applies to the Chinese National Standard (CNS) A4 specification (X297 mm) 509694 A7 B7 V. Description of the invention (47) The ligand of the mismatched catalyst, and The free-state organic phosphite ligand present in the reaction medium of the method of the present invention is used in two ways. In addition, it should be understood that although the metal-organophosphite coordination dislocation catalyst is compatible with the organic phosphite ligand Ligands, and any excess free-state organic phosphite ligands that are preferably present in a particular method of the invention, are usually the same type of ligand, but different types of organic phosphite ligands, and two Mixtures of one or more different organic sulfite ligands can be used for any purpose in any particular method if required. Metal-organophosphite complexation catalysts exist in the reactions of the specific methods of the present invention The amount in the medium need only be the minimum amount necessary to provide the concentration of the specific metal to be used, and it will be supplied as the basis for at least the catalytic amount of metal necessary to catalyze the specific method desired. In general, the metal concentration in the range of about 1 part per million to about 10,000 parts per million is calculated as the free state metal, and the ligand to metal mole ratio in the catalyst solution The range is from about j • 1 or lower to about 200 · · 1 or larger. For most methods, it should be enough for the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economics. In addition to dislocation catalysts, the method of the present invention, and particularly the hydroformylation method, can be performed in the presence of a free-state organic phosphite ligand. Although the method of the present invention can be carried out with any desired free-form organic phosphite ligands, the use of free-form organic phosphite ligands is not absolutely necessary. Therefore, in general, the amount of ligand is about U Moore or lower per mole of metal (eg germanium) present in the reaction medium, to about 100 Moore or higher if needed, for most For the purpose, especially with regard to germanium-catalyzed hydroformylation, the degree of appropriateness of household financial standards (CNS) A4 50-509694 A7 B7 V. Description of the invention (48) should be suitable; the amount of the ligand It is the sum of the amount of ligands bound (mismatched) to the metal present and the amount of ligands present in the free state (not mismatched). Of course, if necessary, supplementary ligands can be supplied to the reaction medium of this method at any time and in any suitable manner to maintain a predetermined amount of free-state ligands in the reaction medium. As indicated above, the catalyst may be in a heterogeneous form during the reaction and / or during product separation. This catalyst is particularly advantageous in the hydroformylation of olefins to produce high boiling points or heat-sensitive aldehydes, so the catalyst can be separated from the product by filtration or decantation at low temperatures. For example, the rhodium catalyst can be attached to a support so that the catalyst remains in its solid form during the two stages of hydroformylation and separation, or it can be dissolved in a liquid reaction medium at high temperatures and then precipitate upon cooling . The following is used as an illustration, the germanium catalyst can be impregnated on any solid support, printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page), such as inorganic oxides (meaning Alumina, silica, titania or oxide), carbon or ion exchange resin. The catalyst can be supported or sandwiched in the pores of zeolite, glass or clay; the catalyst can also be dissolved in the liquid film coated with the stagnant stone or glass pores. Such a catalyst using zeolite as a support is particularly advantageous for producing one or more regioisomeric aldehydes with high selectivity, which is determined by the pore size of the zeolite. Techniques for carrying the catalyst on a solid, such as initial wetting, are known to those skilled in the art. The solid catalyst thus formed may still be mismatched with one or more of the ligands defined above. For a description of such solid catalysts, refer to, for example, J. Mol · Cat 1 " 1, 70, 363, 368; Catal. Lett. 1991, 8, 209-214; J. Organomet. Chem, 1991, 403, 221-227; Nature, 1989, 339, 454-455; J. Catal · 1985, 96, 563-573; J. Mol. Cat. 1987, -51-This paper size applies to Chinese National Standard (CNS) A4 Specifications (210X2 ^^ 509694 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (49) 39, 243-259 Cellulose or polyphenylene, as described in J. Mol. Cat 1990, 63, 213-221. Metal (eg, rhodium) catalysts can pass through organic phosphorus-containing ligands, such as being incorporated into polymers The phosphite is connected to an insoluble polymer support. The supported catalyst is not limited by the choice of polymer or phosphorus-containing species incorporated in it. For a description of the catalyst supported by the polymer, see For example: J. Mol. Cat. 1993, 83? 17-35; Chemtech 1983, 46; J. Am. Chem. Soc. 1987, 109, 7122-7127 〇 In the heterogeneous catalyst mentioned above In the catalyst, the catalyst can maintain its heterogeneous form during the entire method and the catalyst separation method. In another specific embodiment of the present invention, the catalyst can be supported on a polymer, which due to its molecular weight It can dissolve in the reaction medium at high temperature, but precipitate on cooling, so it helps to separate the catalyst from the reaction mixture. Such "soluble" polymer-supported catalysts are described in, for example, Polymer! 1992 , 33, 161; J. Org. Chem. 1989, 54, 2726-2730. The hydroformylation reaction is more preferably carried out in a slurry phase due to the high boiling point of the product and to avoid decomposition of the aldehyde product. Then The catalyst can be separated from the product mixture, for example by filtration or decantation. The reaction product fluid can contain heterogeneous metal-organotransferate coordination catalysts such as a slurry or at least a portion of the reaction product fluid It may be contacted with a fixed heterogeneous metal-organic phosphite coordination dislocation catalyst during a specific method. In a specific embodiment of the present invention, a metal-organic phosphite coordination dislocation contact may be contacted. Medium in -52- paper ruler Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) # >

Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs of the People's Republic of China. 509694 V. Description of the invention (50) The reaction product is formulated into a slurry. The allowable reaction conditions which can be used in the method of the present invention are, of course, selected according to the desired specific synthesis. Such process conditions are known in the art. All methods of the present invention can be performed according to conventional procedures known in the art. Illustrative examples of reaction conditions for carrying out the method of the present invention are described in, for example, the Encyclopedia of Chemical Technology, Fourth Edition, Chinese. The relevant parts are incorporated herein by reference. Depending on the particular method, the operating temperature range can be from about _80. (: Or lower, to about 600 τ or higher, and operating pressure can range from about 1 psig or lower, to about 10,000 psig or higher. The present invention < The time required to produce the desired product. The exact reaction time used depends in part on factors such as temperature, pressure, raw shellfish and ratio, etc. The reaction time is usually about half an hour to about 200 hours or More, and preferably less than about one hour to about 10 hours. The method of the present invention, and preferably the hydroformylation method, can be used for metal-organic phosphite coordination catalysts. It is carried out in the presence of an organic solvent. This solvent may also contain dissolved water reaching the saturation limit. Depending on the particular catalyst and reactants used, suitable organic solvents include, for example, alcohols, alkanes, alkenes, alkynes, ethers Compounds, aldehydes, ketones, esters, amines, amines, aromatic hydrocarbons, and the like. Any suitable solvent that does not unduly and adversely interfere with the intended method can be used, and such Solvents can include methods hitherto commonly used for known metal catalysis Among them. Increasing the dielectric constant or polarity of the solvent usually has a tendency to increase the reaction rate. Of course, if necessary, a mixture of one or more different solvents can be used. Obviously, the solvent-53 paper scale is applicable to China Standard (CNS) 8 4 specifications (210X297 mm) '-(Please read the precautions on the back before filling out this page) Order Φ Printed by the Central Bureau of Standards of the Ministry of Economic Affairs for consumer cooperation 509694 A7 * ----.一 —__ Β7 V. Description of the invention (51). Shiben ^ Ming is not important. Five is only necessary to make the reaction medium have a specific metal concentration required for the method of setting.-Generally speaking, when two agents, The range from about 5% by weight to up to about 5% by weight is based on the total weight of the starting material of the reaction mixture. The method of the present invention can be used to prepare substituted and unsubstituted optically active Optically active compounds. Illustrative examples of compounds made by the method of the present invention include, for example, substituted and unsubstituted alcohols or phenols · amines; haloamines; ethers or epoxides; esters; ketones class ; Aldehydes; and nitriles. ^ Illustrative examples of suitable optically active and non-optically active compounds (including the starting material compounds as described above) prepared by the method of the present invention, including in Wonder _ Othmer Encyclopedia of Chemical Technology, Fourth edition, permissible compounds described in 19%, relevant parts of which are incorporated herein by reference, and Merck Index, Encyclopedia of Chemicals, Drugs, and Biologicals, Eleventh Edition, 1989 Permissible compounds, the relevant parts of which are incorporated herein by reference. I The desired product of the present invention can be recovered in any conventional manner, and one or more separators or separation zones can be used in any specific method to extract from it. The desired reaction product is recovered from the crude reaction product fluid. Suitable separation methods include, for example, solvent extraction, crystallization, distillation, vaporization, wiping film evaporation, falling film evaporation, and the like. It may generally be desirable to remove the product from the crude reaction mixture as it is formed using a capture agent as described in the published Patent Cooperation Treaty Patent Application WO 88/08835. A preferred method of separating the product mixture from the other components of the crude reaction mixture is by membrane separation. This type of membrane separation can be based on US Patent Nos. 5,43,194, and co-pending US patent applications filed on May 5, 1995.-54-This paper size is applicable to Chinese national standards (CNS> A4 specification (210X297) Mm) One ~ --------- I * ------, 1T ------ 0 (read first. Please read the notes on the back before filling out this page) 509694 A7 B7 Economy Printed by the Ministry of Standards and Staff ’s Consumer Cooperatives. 5. The description of the invention (52 08 / 430J90 detailed above is achieved. The method of the present invention can use, for example, fixed bed reactors, fluidized bed reactors, continuous stirring. Tank reactor (CSTR) or slurry reactor. The optimal size and shape of the catalyst depends on the type of reactor used. Generally, for fluid bed reactors, small spherical catalyst particles are more suitable. Good, because it is easy to fluidize. With fixed bed reactors, larger catalyst particle systems are preferred, so the back pressure system in the reactor is kept reasonably low. At least one of the employed in the present invention Reaction zone, which can be a single container or can contain two or more discrete containers The at least one separation zone used in the present invention may be a single container or may include two or more discontinuous containers. The at least one scrubbing zone used in the present invention may be a single container or may include Two or more discontinuous vessels. It should be noted that the reaction zone and separation zone used in this article may exist in the same container or in different containers. For example, reactive separation techniques such as reactive distillation, Reactive membrane separation, etc., can occur in the reaction zone. The method of the present invention can be carried out in a batch or continuous manner, wherein the unconsumed starting material is recycled if necessary. This reaction can be performed in a single reaction zone Either in multiple reaction zones, in series or in parallel, or in a batch or continuous manner in an elongated tubular zone or a series of such zones. The construction materials used should be The substance is inert, and the equipment should be able to resist the reaction temperature and pressure. Failure during the reaction: batch mode or continuous mode, introduction and / or adjustment are introduced into the reaction zone. The starting material or the device of the component amount can be suitably used in this method, especially to maintain the required molar ratio of the starting material. The reaction steps can be adapted by private recording scales (please read the notes on the back before filling in (This page)

1T • —--- 2 1 _... 2_- Chuan 9694 A7 B7 V. Description of the invention (53) The amount of one of the starting materials is added to the other. It is also possible to combine the reaction steps by simultaneously adding starting materials. When complete conversion is not desired or is not available, the starting material can be separated from the product, for example by distillation, and then the starting material can be recycled back into the reaction zone. This method can be carried out in glass-lined stainless steel or similar types of reaction equipment. The reaction zone may be equipped with one or more internal and / or external heat exchangers to control improper temperature fluctuations or prevent any possible "runaway" reaction temperatures. The process of the invention I may be carried out in one or more steps or stages. The exact number of reaction steps or stage 4 is the best compromise between capital and achieving high catalyst selectivity, activity, fate, and ease of implementation, as well as the reactivity of the starting material in question, and The stability of the starting material and the desired reaction product to the reaction conditions is at the disposal. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs in a specific embodiment, which can be used in the hydroformylation method of the present invention, and can be reacted in multiple stages This multi-stage reactor can be designed, for example, as described in the co-pending US patent application serial number (D_17425_1}, filed on the same date as this case. It has an internal physical barrier, which establishes more than one theoretical reaction stage in each container. In fact, it is like having a reaction vessel inside a single continuous stirred tank. Multiple reactors are the same. Multiple reaction stages in a single container are a cost-effective way to utilize the volume of the reaction container. It will significantly reduce the number of containers required to achieve the same result in other ways. Less Rongtai will reduce The overall capital required and the maintenance of individual containers and sandboxes.-(Please read the precautions on the back before filling out this page.) Thai paper size is applicable to Chinese National Standard (CNS) A4 (210x297 mm) Central Standard of the Ministry of Economic Affairs. Printed by the Bureau's Consumer Cooperatives 509694 A7--B7 V. Description of the Invention (Private) Compound I can be used in a better method of the present invention, which is hydroformylation. It may go through organic phosphites Examples of such hydrolytic degradation of the ligand and catalytic inactivation of the metal-organophosphite complex complex catalyzed hydroformylation method include, for example, US Patent Nos. 4,148,830; 4,593,127; 4,769,498; V17J75; 4,774,361; 4,885,401; 5,264,616; 5,288,918; 5,360,938; 5,364,950; and 5,491,266, the disclosures of which are incorporated herein by reference Therefore, the hydroformylation treatment technology of the present invention can correspond to any known treatment technology. The preferred method is a method involving the catalytic liquid recirculation hydroformylation. Generally speaking, this catalytic liquid recycles hydrogen The formication method involves the production of acids. The method is to make the olefin unsaturated compound, carbon monoxide and hydrogen in the presence of a metal-organophosphite complexing catalyst, and it also contains the catalyst and the ligand. Reaction in a liquid medium of an organic solvent. Free-state organic phosphite ligands are also preferably present in the liquid hydroformylation reaction medium. The recycling procedure generally involves continuously or intermittently from a hydroformylation reactor (Meaning the reaction zone), take out a part of the liquid reaction media containing catalyst and aldehyde products and recover the acid products from it using composite films, such as in US Patent 5,430,194 and 1995 The co-pending U.S. patent application serial number 08 / 43〇, 79, which was filed on May 5th, is disclosed herein for reference, or by a more conventional and better method, In one or more stages, in an appropriate manner, at a normal pressure, reduced pressure or high pressure, in an individual distillation zone, it is distilled (that is, vaporized and separated), and the non-volatile metal catalyst containing the residue is re- Circulate to the reaction zone, such as the Chinese National Standard (CNS) A4 rule at the I paper scale ^ 7 ^ * 1 ---- ------ Γ-. 0 ^-(Read the note on the back first Please fill in this page again) Order 509694 V. Description of the invention (A7 B7 55 Please read the precautions on the back before disclosure in US Patent 5,288,918. Condensation of volatile substances, and their progressive recovery, such as by further distillation, can be carried out in any conventional manner. If f is required, the crude acid product can be advanced for further purification and / or structure separation. Any recovered reactants, such as olefin starting materials and synthesis gas, can be recycled to the hydroformylation zone (reactor) in any desired manner. The recovered metal catalyst containing the thin-film-separated residual liquid 'or the recovered non-volatile metal catalyst containing such vaporized separation residues can be recycled to the hydroformylation in any conventional manner desired. Zone (reactor). Printed in a preferred embodiment by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economics, the hydroformylation reaction product fluid that can be used herein is any fluid that contains any fluid derived from any corresponding hydroformylation method, which contains i A few amounts of four different main ingredients or components, that is, aldehyde product, metal-organic phosphite coordination catalyst, free-state organic phosphite ligand, and the catalyst and the free state The organic solvent used for the ligand is corresponding to the component used and / or prepared by the hydroformylation method, and the starting material of the hydroformylation reaction mixture can be derived therefrom. It should be understood that the hydroformylation reaction mixture composition that can be used herein can and usually contains a relatively small amount of other ingredients, such as those that have been deliberately used in the hydroformylation process or formed on the spot during the process . Examples of such ingredients that may also be present include unreacted olefin starting materials, carbon monoxide and hydrogen, and product types formed on the spot, such as saturated hydrocarbons and / or unreacted isomerization corresponding to olefin starting materials Olefins, and high stagnation point liquid aldehyde condensation by-products, and other inert co-solvent types of substances or hydrocarbon additives, if used. This paper size applies the Chinese National Standard (CMS) A4 specification (210X 297 mm) 509694 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention (56) ^ — " Can be used in the present invention Substituted or unsubstituted olefin reactants in chemical methods (and other suitable methods), including optically active (pre-palladium and anti-palladium) and non-optically active (non-palladium) alkane unsaturated compounds, It contains 2 to 40 carbon atoms, compared with 4 to 20 carbon atoms. Such fluorene hydrocarbon unsaturated compounds may be terminally or internally unsaturated, and have a linear, branched or cyclic structure, as well as olefin mixtures, such as oligomerization obtained from propane, butylene, isobutylene, etc. ( For example, the so-called dimerization, trimerization, or tetramerization, etc., as disclosed in US Pat. Nos. 4,518,809 and 4,528,403). Furthermore, such a fluorene compound may further contain one or more ethylenically unsaturated groups, and a mixture of two or more different fluorinated hydrocarbon compounds may of course be used as a starting material if necessary. For example, a commercially available alpha olefin containing four or more carbon atoms may contain a smaller amount of the corresponding internal olefin and / or its corresponding saturated hydrocarbon, and such a commercially available olefin need not be purified prior to the reaction. Mixtures of olefin starting materials which can be used in the hydroformylation reaction, and illustrative examples include, for example, mixed butenes, such as the raffinates I and Π. Furthermore, such hydrocarbon-associated unsaturated compounds and corresponding products derived therefrom may also contain one or more groups or substituents that do not unduly and adversely affect the method of the invention, such as in US Patent 3,527,809. , 4,769,498, etc. The present invention is particularly useful for non-palladium α-olefins containing 2 to 30, preferably 4 to 20 carbon atoms, and non-palladium internal olefins containing 4 to 20 carbon atoms, and the like. A mixture of α-olefins and internal olefins as a starting material, arginine, is produced to produce non-optically active acids. Examples of π and internal olefins include, for example, ethylene, propane, 1-butene, 1-pentamidine, L-hexane, 1-octyl, 1-nonyl, 1-decane, 1-undecene r, 1_dodecene ·, 1--13 ______-. fSQ- _ This paper size applies to the Chinese national standard (CNsTa4 specification (210X297: mm) ~~~~-(Please read the notes on the back first Fill out this page again), tr 509694 A7 V. Invention description (57 printed by women's consumer cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, μ tetradecene, 1-pentadecene, 1-hexadecene, μ 17-ene, 1 -Eighteen women, 1-nonadecene, μ eicosene, 2-butene, 2-methylpropene (isobutylene), methylmethylbutene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 2-octene, hexene, propylene dimer, propylene trimer, propylene tetramer, butadiene, pentadiene, isoprene, 2-ethyl small Hexene, styrene, 4-methylstyrene, isopropylstyrene, 4-tert-butylacetophenone, π-methylstyrene, tert-butyl-α-methylbenzene Ethylene, 1,3-diisopropene-based benzene, 3-phenyl_1-propylene, 1, 'hexadiene, 1,7-octadiene, 3 _Cyclohexyl-butadiene 'and its analogs, and 1,3-dienes, butadiene, alkyl enoates such as methyl pentenoates, alkenyl alkanoates, alkenyl alkyl ethers Enols such as pentanol, aldehydes such as pentenal, and the like, such as allyl alcohol, propyl butyrate, hexenyl alcohol, octyl alcohol, vinyl acetate, Allyl acetate, 3-Butene acetate, Ethyl propionate, Allyl propionate, Methyl methacrylate, Vinyl ethyl ether, Ethyl methyl ether, Allyl ethyl Ether, n-propyl-7-octanoate, 3-butanol, 5-hexenamidamine, eugenol, isoeugenol, safrole, isosfrole, anisinol, 4-allyl tolyl ether, indene , Lemon olein, wolfberry, -cyclopentadiene, cyclooctadiene, pinene, linalool, and the like. It can be used to produce a mixture of palmar isomer products, and can be used in the present invention. Exemplary examples of palmitic and palmitic olefins used in asymmetric hydroformylation methods (and other incorrect and T-scale methods) include the following 4 Scribble expressions: R1 R3 \ / 3 c = c Ώ / \ 1¾ R4 (XII) (Please read the precautions on the back before filling in this page) k Packing and binding paper size is applicable to Chinese National Standard (CNS) A4 specification (21 OX297 mm) 509694 A7 B7 V. Description of the invention (58), wherein R2 and R4 are the same or different (provided that Ri is different from R2 'or r3 is different from r4) and is selected from hydrogen; alkyl; substituted alkyl; The substitution is selected from the group consisting of dialkylamino groups such as benzylamino and dibenzylamino, alkoxy groups such as methoxy and ethoxy, fluorenyl groups such as ethoxy, fluorenyl, nitro, nitrile, and thio , Carbonyl, carboxamido, carboxaldehyde, carboxyl, carboxylate; aryl, including phenyl; substituted aryl, including phenyl, the substitution is selected from alkyl, amine, including alkylamino and diamine Alkylamino groups, such as benzylamino and dibenzylamino groups, alkoxy groups such as methoxy and ethoxy, alkoxy groups such as ethoxy, alkoxy, nitrile, nitro, carboxyl, carboxyl Aldehydes, carboxylic esters, carbonyls and thios; alkoxy groups, such as ethoxy; alkoxy groups, such as methoxy and ethoxy; amine groups, including alkylamino and dialkylamino groups, such as Benzylamino and dibenzylamino; fluorenylamino and difluorenylamino, such as ethylaminobenzylamino and diethylamino; nitro; carbonyl; nitrile; carboxyl; carboxamido; carboxaldehyde; Carboxylic acid esters, and alkyl, such as methyl mercapto. It should be understood that the previous definitions of unisexuality and palmitic hydrocarbons also include molecules in which the R groups in the above formula are connected to each other to form a cyclic compound, such as 3-methyl-1-cyclohexene and the like. Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Masonry Consumer Cooperative (please read the notes on the back before filling out this page). It can be used in the asymmetric hydroformylation method (and other asymmetric methods) of the present invention. Illustrative examples of palm olefin compounds include, for example, p-isobutylstyrene, 2-vinyl-6-methoxynaphthylnaphthalene, 3-ethylfluorenylthenylfluorenone, 4-ethylenylphenyl-2 -p-sedenyl ketone, 4-ethylammonium-based biphenyl, 4- (1,3_dihydro smalloxy_2H_isoindole_2_yl) phenethylfluorene, 2-vinyl- 5-benzylidenepyrimidine, 3-vinylphenylphenyl ether, propenylbenzene, isobutyl-4-propanylbenzene, phenylethylfluorenyl ether, and the like. Other olefin compounds, including substituted arylethylene, for example, in the United States patent 5 price, [paper rule national standard A4 & i (2Ι0 × 2 ~: 厘) printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 509694 kl ---________ B7 5 2. Description of the invention (59) 5,360,938 and 5,491,266, the disclosures of which are incorporated herein by reference. Examples of suitable substituted and unsubstituted olefin starting materials include the permissible substituted and unsubstituted fluorene compounds described in Kirk-Othmer, Encyclopedia of Chemical Technology, Fourth Edition, 1996, which Relevant parts are incorporated herein by reference. As noted, the method of formazanization of the present invention involves the use of a metal-organophosphite coordination dislocation catalyst as described above. This hydroformylation catalyst can be in a homogeneous or heterogeneous form during the reaction and / or during product separation. Of course, a mixture of such catalysts can also be used if necessary. The amount of metal-organophosphite coordination dislocation catalyst present in the reaction medium of the specific hydroformylation method covered by the present invention need only be the minimum amount necessary to provide the specific metal concentration to be used, And it will be supplied as the basis for at least the catalytic amount of metal necessary for the catalyzed special hydromethylation process involved, such as those disclosed in the patents mentioned above. Generally speaking, the concentration of metal (such as rhodium) in the hydroformylation reaction medium is within the range of about 10 parts per million to about 1000 parts per million. In terms of method, it should be sufficient, however, it is usually preferred to use about 10 to 5000 parts of metal, such as germanium per million parts, and more preferably 25 to 350 parts of metal, such as germanium per million parts. In addition to metal-organophosphite coordination dislocation catalysts, free-state organic phosphite ligands (meaning, ligands that are not complexed with metals) can also be present in the hydroformylation reaction medium. This free-state organic phosphite ligand may correspond to any of the above-defined organic phosphites that can be used herein. 4 ------ This paper size applies to Chinese National Standard (CNS) A4 specifications ( 210X297 mm) I — — — (Please read the precautions on the back before filling out this page)-Equipment ·-, 11 Printed by the Employees' Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs 509694 A7 ___ ___B7 V. Description of Invention (60) I Ligand. This free organic phosphinate ligand is preferably the same as the organic brickinate ligand used in the metal-organophosphite coordination dislocation catalyst. However, these ligands need not be the same in any particular method. The method of hydroformylation according to the present invention may include a free organic sulfonic acid that is about 0.1 mole or less per mole of metal in the hydroformylation reaction medium to about 1 mole or more. Ligand. The chloroformation method of the present invention is preferably carried out in the presence of about 1 to about 50 moles of organic phosphite ligands, and more preferably about 0.001 to about 5% for organic polyphosphites. 4 moles of organic polyphosphite ligands, based on the metal present in the reaction medium per mole; the amount of the organic phosphite ligands is the amount that is bound (mismatched) to the metal present The sum of the amount of the organic phosphite ligand and the amount of the free state (not mismatched) organic phosphite ligand that exists. Since it is better to hydroformylate non-palladium olefins to produce non-optically active aldehydes, the better organic phosphite coordination system is a non-palladium type organic phosphite ligand, Especially those covered by the above formulae, and more preferably those of formulae (VI) and (IX) above. Of course, if necessary, supplementation or other organic phosphite ligands can be supplied to the reaction medium of the hydroformylation method at any time and in any suitable manner, for example, to maintain a predetermined amount of free state in the reaction medium Ligand. The reaction conditions for the hydroformylation process encompassed by the present invention may include any suitable form of hydroformylation conditions hitherto used to produce optically active and / or non-optically active aldehydes. For example, the total gas pressure of hydrogen, carbon monoxide, and hydrocarbon-associated starting compounds in the hydroformylation process may range from about i to about 10,000 psia. However, in general, this method is better for hydrogen and carbon monoxide. The paper size is applicable to Chinese countries. A4 size (210x7 ^ 1 丨 1 · —— (read the precautions on the back before filling in this page)

Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, 1T 509694 A7 ______ B7 V. Description of the invention (61) ^ and the total gas pressure of the fluorene starting compound is below about 2000 psia, and more preferably below about 500 psia operating. The minimum total pressure is mainly limited by the amount of reactants necessary to obtain the desired reaction rate. More specifically, the carbon dioxide partial pressure of one of the hydrogen methylation methods of the present invention is preferably about 1 to about 1000 pSia, and more preferably about 3 to about 800 psia, and the hydrogen partial pressure is preferably about 5 to about 500. psia, and more preferably about 10 to about 300 psia. Generally speaking, the molar ratio of gaseous hydrogen to carbon monoxide h2: CO can cover from about 1:10 to 100 ·· 1 or higher. : 10 to about 10: 1. Furthermore, the hydroformylation method can be performed at a reaction temperature of about -25 ° C to about 200 ° C. Generally speaking, about 50. (: Hydroformylation reaction temperature to about 120 ° C is preferred for all types of fluorene hydrocarbon starting materials. Of course, it should be understood that when a non-optically active aldehyde product is desired, It uses non-palladium type hydrocarbon starting materials and organic phosphite ligands, and when optically active acid products are desired, it uses pre-palladium or palmity type olefin starting materials and organic Phosphite ligands. Of course, it should also be clear that the hydroformylation reaction conditions used are governed by the type of aldehyde product desired. The hydroformylation methods covered by the present invention are also available for metal- The organic phosphite coordination catalyst and free organic organic phosphite ligand are used in the presence of an organic solvent. This solvent may also contain dissolved water to reach the saturation limit. Depending on the specific catalyst used and Depending on the reactant, suitable organic solvents include, for example, alcohols, alkanes, amidines, alkynes, ethers, aldehydes, higher boiling acid condensation by-products, ketones, esters, ammoniums, tertiary amines , Aromatics, etc. will not interfere inappropriately and adversely Any suitable solvent for the hydroformylation reaction can be used, and such solvents can include those disclosed so far (please read the precautions on the back before filling out this page) One Pack ·-Order Staff Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs Print A7 5. Description of the invention (wrestling)-~ '~' '-One " is used for those who have known metal-catalyzed hydroformylation reactions. If necessary, it can be used or different; a mixture of agents. Generally speaking, with regard to the manufacture of non-palladium (bright light to live) products, it is preferred to use acid compounds corresponding to the acid product to be produced and / or higher-boiling aldehyde liquid condensation by-products as the main products. Organic, cereal, as commonly used in this technology. This acid condensation field 1J product can also be pre-formed when needed, and used accordingly. A better solvent that can be used in the aftergas k, its description Examples include ketones (such as acetone and methyl ethyl _), g compounds (such as ethyl acetate), hydrocarbons (such as toluene), nitro hydrocarbons (such as nitrobenzene), and ethers (such as tetramethylfuran). (ΤΗρ)) and cyclamidine. Appropriate agents are disclosed in the United States. No. 5,312,996. The amount of solvent used is not critical to the present invention, and only needs to be sufficient to solubilize the catalyst and free-state ligand of the hydroformylation reaction mixture to be treated. The f of the agent may cover a range from about 5% by weight to up to about 99% by weight, based on the total weight of the starting material of the hydroformylation reaction mixture. ′ Therefore, illustrative examples of non-optically active aldehyde products include For example, propionaldehyde, n-butyraldehyde, iso-butyraldehyde, n-pentamidine, 2-methyl-butyraldehyde, hexanal, hydroxyhexanoic acid, 2-methylvaleraldehyde, heptaldehyde, 2-methylhexanole Aldehyde, octanal, 2-methyl + heptanal, nonanal, 2-methyl-1-octanal, 2-ethylheptanal, 3-propylhexylaldehyde, decanal, adipaldehyde, 2 -Methylglutaraldehyde, 2-methyl adipaldehyde, 3-methylhexadialdehyde, 3-per-propionic acid, 6-synylhexanoic acid, acetic acids, such as fluorene, 3- and 4-pentyl. '5-Methynylpentanoic acid @ base, 2-methyl + nonanoic acid, undecyl aldehyde, 2-methyl small decanal, dodecanal, 2-methyl small undecanal, tridecanoic acid, 2-methyltridecylaldehyde, 2 · ethyl-1 · dodecaldehyde, 3-propyl minor undecanoic acid, paper Zhang scale is applicable to China National Standard (CNS) A4 specification (2ίΟχ29 ”mm) (Please read the notes on the back before filling out this page) -ΙΤ» 509694 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Α7 Β7 V. Description of the invention (63) Pentadecanoic acid, 2-methyl_1-tetradecanoic acid, hexadecanal, 2-methyl pentadecyl, hepta '′, 2-methyl-1-hexadecanoic acid, stearyl, 2-methyl_1-heptadecanal, nonadecanic acid, 2-methyl-1-octadecanoic acid, 2-ethyl-1-heptadecanoic acid, 3-propylhexadecanoic acid, eicosaldehyde, 2 _Methylcanadecanal, behenaldehyde, 2-methyl + icosanic acid, behenic acid, 2-methyl_1-docosaic acid, behenic acid, 2.methyl] _ Thirteen-year-old, twenty-five aldehydes, 2-methyl-1-docosaic acid, 2 · ethyl-μ docosalydehyde, 3-propylpicosuccinic aldehyde, twenty-seven aldehyde, 2_ Methyl-1-octacosanoic acid, diacosanoic acid, 2-methyl-1-octacosanoic acid, 31-acrylic acid, 2-methylicosuccinaldehyde, and the like. Illustrative examples of optically active aldehyde products include (para-isomeric) aldehyde compounds prepared by the asymmetric hydroformylation method of the present invention, such as s_2_ (p-isobutylphenyl) -propionic acid, S -2- (6-methoxy-2-fluorenyl) propanal, S-2- (3-benzylidenephenyl) _propionic acid, S-2- (p-telephenethylphenyl) Propanoic acid, S-2- (3-fluoro-4-phenyl) phenylpropionic acid, S_2- [4- (l, 3-dihydro-1-oxy-2H-isoΘ 卜 朵 -2- Group) phenyl] propanal, S_2_ (2-methylacetaldehyde) -5 benzamidinepyrimidine and the like. Illustrative examples of suitable substituted and unsubstituted aldehyde products include the permissible substituted and unsubstituted aldehyde compounds described in Kirk_Othmer Encyclopedia of Chemical Technology, Fourth Edition, 1996, the relevant parts of which are For reference. As noted above, it is generally preferred to perform the hydroformylation process of the present invention in a continuous manner. Generally speaking, continuous hydroformylation methods are well known in the art, and may involve: hydration in a solvent, a metal-organic phosphite coordination dislocation catalyst, and a free-state organic phosphite coordination In the liquid homogeneous reaction mixture of the body, carbon monoxide and hydrogen are used to make the olefin starting material hydrogen methyl ------------ ^ ~ This paper size is applicable to the Chinese National Standard (CNS) M specification (210X297 mm)- ----- ：-J · install-- (Please read the precautions on the back before filling out this page) Order 9694 Printed by the Consumer Standards Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs 64 A7 B7, Invention Description (^ 化 ' (B) Maintain reaction temperature and pressure conditions that are favorable for the hydromethylation of the hydrocarbon starting materials; When the reactants are used up, supply supplementary amounts of olefin starting materials, oxidative breakdown and hydrogen to the reaction medium And (d) recover the desired aldehyde hydroformylation product in any desired manner. This continuous process can be performed in a single-private mode, meaning that it contains unreacted fluorinated hydrocarbon starting materials and vapors of evaporated aldehyde products Mixture, removed from the liquid reaction mixture It recovers the aldehyde product from it, and supplies the supplemented hydrocarbon starting material, carbon monoxide and hydrogen to the liquid reaction medium for the next one-way use, without recycling the unreacted olefin starting material. The cycle procedure is familiar to horses in this art, and may involve the recycling of liquids that have been separated from the desired acid reaction product < metal-organophosphite complex catalyst fluid, such as in U.S. Patent 4, Disclosed in 148,830, or a gas recirculation procedure, such as disclosed in U.S. Patent 4,247,486, and a combination of liquid and gas recirculation procedures, if required. Disclosure of this U.S. Patent 4,148 83〇4 4247,486 Intrinsics are incorporated herein by reference. The optimal hydroformylation method of the present invention includes a continuous liquid catalyst recycling method. Suitable liquid energy catalyst recycling procedures are disclosed in, for example, U.S. Patent 4,668,651, 4,774,361 '· 5,102,505 and 5,110,990. In one embodiment of the present invention, the other components of the reaction mixture can be separated from the product mixture, and mixed together. Made by any suitable method. Common methods of separation include, for example, solvent extraction, phase separation, 'crystallization, distillation, vaporization', wipe film evaporation, falling film, and similar methods. When the crude reaction mixture is formed, you can use it as described in the published patent cooperation, and please apply for financial support. Weng Peng (please read the precautions on the back before filling this page)

A7 B7 509694 5. The capture agent described in the description of the invention (65), from which the aldehyde product is removed. A preferred method of separating the product mixture from the other components of the crude reaction mixture is by thin-film knife-off. Such membrane separation can be achieved in accordance with the above details as detailed in the US patent and the co-pending US patent application serial number 08 / 430,790 filed on May 5, 2005. As noted above, at the end of the method of the invention (or during its performance) the desired acids can be recovered from the reaction mixture used in the method of the invention. For example, 'recovery techniques disclosed in U.S. Patent Nos. 4,148,830 and 4,247,486 can be used. For example, in a continuous liquid catalyst recycling method, a portion of the liquid reaction mixture (containing aldehyde products, catalysts, etc.) privately removed from the reaction zone may be the reaction product fluid through the separation zone, such as a vaporizer / Separation t ', in which the desired aldehyde product can be separated, condensed and collected in the product receiver from the liquid reaction fluid by distillation under normal pressure, reduced pressure or high pressure in one or more stages' and if required Further purification. Then, the residual non-volatile catalyst containing the liquid reaction mixture can be recycled back to the reaction zone, and if desired, any other volatiles #, such as unreacted olefins, can be dissolved in the liquid reactants. Any hydrogen in it and one after it is separated from the condensed acid product, for example, return to the reaction zone in any conventional manner = after distillation '. It is usually preferred to separate the desired aldehydes from the catalyst-containing reaction mixture under reduced pressure and at low temperature to avoid possible degradation of the phosphite ligands and reaction products. When mono-olefin reactants are also used, their aldehyde derivatives can also be isolated by the methods described above. More specifically, the distillation and separation of the desired aldehyde product from the reaction product fluid containing the metal-organic phosphite mixing catalyst can be performed in any desired paper county (CNS) iron grid (21GX29 ^ t (please first Read the notes on the back and fill out this page}

A7 B7 V. Description of the invention (66 Tongdang temperature.-It is generally recommended that such steaming halls be carried out at a relatively low temperature, such as less than 150. (:, and more preferably about 400 to about 14 oΌ At the temperature of Fanyuan, it is also generally recommended that such aldehyde distillation be carried out under reduced pressure, for example, each involving a low hysteresis aldehyde (for example, when C4 is reached, the total gas pressure is substantially two times lower than that during hydroformylation). The total gas pressure used, or when high-boiling aldehydes (such as & or larger) are involved, under airspace. For example, the general implementation is to accept the liquid reaction product medium removed from the hydroformylation reaction zone. Reduce the pressure to volatilize most of the unreacted gas that has been dissolved in the liquid medium, compared with the concentration of the synthesis gas in the hydroformylation reaction medium, which currently contains a much lower concentration of the synthesis gas. Bring it to a distillation zone, such as a vaporizer / separator, where the desired aldehyde product is distilled. In general, Fan Yuan goes from emptying pressure to a distillation pressure up to a total gas pressure of about 50 psig. Words should be enough. Removal Treatment As described above, the present invention is based on the discovery of hydrolytic decomposition and inactivation of the germanium catalyst. As discussed herein, one or more acid shifts sufficient to remove at least some amounts of phosphoric compounds from the reaction product fluid can be used. Elimination of substances, treatment of at least a portion of the reaction product fluid derived from the method of the present invention and also containing phosphoric compounds formed during the method is prevented or reduced. Due to metal salt contaminants in the reaction product fluid, such as Iron, zinc, salt, etc. can undesirably promote the self-condensation of aldehydes, so the advantage of the present invention is that we can use the acidity removal ability of certain acid removal substances, and transfer the least metal salt to the reaction product In the fluid. One or more acids are used to remove substances to remove the metal-organophosphite complex complex catalyzed by the method ___-69-This standard is suitable for financial institutions (CNS) A4 Specification (21〇 × 29ϋ ％)-'(Please read the notes on the back before filling * Pack-: Write this page] Printed by the Central Consumers ’Cooperative of the Ministry of Economic Affairs 509694 A7 B7 printed by the Industrial and Commercial Cooperatives V. Description of the invention (67) '^ ^ Phosphate compounds to prevent and / or reduce the hydrolytic degradation of organic phosphites and their metal-organic phosphites The inactivation of the coordination mismatch catalyst is disclosed in the co-pending US patent application serial number (D_17652), which was filed on the same date as the present case, and its disclosure is incorporated herein by reference. Tritification) remove at least some amount of phosphonic acid compounds, such as I ^ PO3, uronic acids such as hydroxyalkylphosphonic acid, H3po4, etc., to allow us to control the acidity of the formazan reaction reaction medium, so by preventing Or reduce the hydrolytic decomposition, stabilize the usable organic phosphite ligands. The necessity of controlling the acidity I in the metal-catalyzed hydroformylation promoted by the organic phosphites has been explained above. Therefore, the object of the present invention is to remove or reduce excessive acidity from the catalyst system so as to maintain a proper acidity in the reaction product fluid so that the consumption of the usable organic phosphite ligands will not be reduced. At an unacceptable rate, it is hydrolyzed to degrade 'while maintaining catalyst activity to the extent of production. The best way to adjust such acidity provided by the present invention is to remove such phosphoric acid from the reaction product fluid in one or more acid removal zones containing one or more acid removals. In this way, the acidic substance is extracted into the water, as 7F is disclosed herein, 'this is different from merely removing and / or neutralizing and leaving it in the reaction medium', thus avoiding the accumulation of such removed and / Or by-products of neutralization 'and other secondary chemical treatments that may be necessary, or accumulation of salt deposits in the reaction zone, separation zone and / or scrubbing zone. Treatment of the reaction product fluid containing metal-organophosphite coordination catalyst with water can not affect the reaction to generate the reaction inappropriately and adversely------70 -__ This paper size Applicable towels_Home Standards (CNS) A4 Specification (21GX297: L) One " '— " (Please read the precautions on the back before filling out this page} 装--州 州 694 μ Β7 Central Ministry of Economic Affairs 榡The prospective employee consumer cooperative prints the invention description (68) any desired suitable method or method for the basic hydroformylation process of the product fluid. For example, this water treatment can be for all or any of the parts to be treated and has been removed from At least one reaction zone or at least one separation zone is removed to enter the desired reaction product fluid in at least one scrubbing zone. The treated contact water may then be sent to one or more acid removal zones or Return at least one reaction zone * or at least one separation zone. Alternatively, water can be sprayed or otherwise added to at least one reaction zone or at least one separation zone to achieve acidity control. Then, the Formed water The layer is decanted from the reaction product fluid. The present invention relates to the use of water, which is particularly applicable to a continuous liquid catalyst recycling method for hydrogen methylation, which uses the invention of US Patent 5,288,918, which includes a catalytically active reinforcing additive The method is performed in the presence of a type of additive selected from the group consisting of added water, weakly acidic compounds (such as bisphenol), or both added water and weakly acidic compounds. This reinforcing additive is used to help selective hydrolysis And to prevent the accumulation of unwanted monophosphite by-products, which can be formed during certain processes, and which can poison metal catalysts, as explained therein. However, it should be understood that the present invention The "preferred method" means a specific embodiment including preventing and / or reducing the hydrolytic degradation of the organic phosphite ligand and the inactivation of the metal-organophosphite coordination catalyst, in the form of (a ) Treating at least a portion of the hydroformylation in at least one scrubbing zone with water sufficient to remove at least some amount of phosphoric acid compound from the reaction product fluid The reaction product fluid containing the phosphoric acid compound formed during the method and (b) in at least one acid removal zone contains at least a part of the reaction from the reaction. Standards are applicable to Chinese National Standard (CNS) A4 specifications (210 × 297 mm) (Please read the notes on the back before filling out this page) 509694 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (69) Product fluid The water of the phosphoric acid compound removed from the water is treated with one or more acid removal substances sufficient to remove at least some amount of the phosphoric acid compound from the water. This method is still considered to be basically a "non-aqueous" method, This means that any water present in the reaction medium is not present in an amount sufficient to cause the reaction or the medium is considered to contain a separate aqueous or aqueous phase or layer in addition to the organic phase. Furthermore, it should be understood that another preferred method of the present invention, which includes specifics for preventing and / or reducing the hydrolytic degradation of organic phosphite ligands and the inactivation of metal-organophosphite complexation catalysts Embodiments, which are introduced into the at least one reaction zone and / or at least one separation zone by removing at least several amounts of one or more acid-removing substances of phosphoric acid compounds from the reaction product fluid, To treat at least a portion of the reaction product stream m derived from the process and also containing phosphoric compounds formed during the process, it is also tolerated as essentially a " non-aqueous " process. Thus, for example, water can be used to treat a continuous liquid catalyst to recycle all or part of the reaction product fluids of the hydromethylation process, which is removed from the reaction zone at any time before or after the aldehyde product is separated therefrom. except. The water treatment is more preferably related to the treatment of all or part of the reaction product fluid, which is obtained after the desired acid product has been distilled, for example, when the reaction product fluid is recycled to the reaction zone. For example, a preferred mode is to recycle all or part of the injury (such as slipstream) to the reaction product muscle of the reaction zone, just before the catalyst containing the residue enters the reaction zone continuously. Through a liquid extractor containing water. Therefore, it should be clear that I want you to use 7k _ tian; Everyone will treat the feet with metal _ organic ya (please read the precautions on the back before filling this page)

509694 A7 B7 V. Description of the Invention (70) The reaction product fluid of phosphate complex coordination catalyst, in addition to the catalyst complex and its organic solvent, may contain products, free-state organic phosphite ligands, and The reactant and any other ingredients or additives of the reaction are consistent with the reaction medium of the method used to derive the reaction product fluid. Furthermore, removal of the desired aldehyde product can cause the concentration of other components of the reaction product fluid to increase proportionally. Therefore, for example, the concentration of an organic phosphite ligand in a reaction product fluid containing a metal-organophosphite coordination dislocation catalyst to be treated with water according to the method of the present invention may cover about 0.005 and 15 weight The range between percentages is based on the total weight of the reaction product fluid. The ligand concentration on this basis is preferably between 0.01 and 10 weight percent, and more preferably between about 0.05 and 5 weight percent. Similarly, the concentration of metal in the reaction product fluid containing metal-organophosphite coordination dislocation catalyst to be treated with water according to the method of the present invention can be as high as about 5000 parts by weight per million parts by weight of the reaction product. The weight of the fluid is the basis. The metal concentration is preferably a weight ratio between about 50 and 2500 parts per million, based on the weight of the reaction product fluid, and more preferably a weight ratio between about 70 and 2000 parts per million. The weight of the product fluid is based. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) The method of contacting the reaction product fluid containing metal-organic phosphite coordination catalyst with water, and the processing conditions For example, the amount of water, temperature, pressure, and contact time are not of critical importance, and obviously only need to be sufficient to obtain the desired result. For example, the process can be performed in any suitable vessel or container, such as any conventional liquid extractor of a suitable device that provides adequate contact between the organic reaction product fluid and water, and can be employed herein. Generally speaking, it is better to use organic reaction product fluid in countercurrent mode ___ -73- ______ This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs System A7-'a__' 'llllllmm-… _ B7 V. Description of the invention (71) Extract the water in the tower through the sieve tray. The amount of water used in the present invention, and the time of contact with the reaction product fluid, need only be sufficient to remove at least some amount of a phosphoric acid compound that will cause the hydrolytic degradation of the desired organic phosphite ligand. The amount of water is preferably sufficient to at least maintain the concentration of such acidic compounds, which is lower than the lower limit content that will cause rapid degradation of the organic phosphite ligands. Any degradation is carried out by a non-hybridizing mechanism "for the amount, such as ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, (,,,,,,,)), (Automata), kinetic-rate-law, Mataperez et al., Journal of Chemical Isolation, Volume VII, Issue 11, November 1987 , As described on pages 925 to 927, rather than by the "catalytic mechanism" described in the paper. Typically, the maximum water concentration is only governed by actual tests. The processing conditions, such as temperature, pressure, and contact time, can also vary greatly, and any appropriate combination of these conditions can be used in this article. For example, lowering one of these conditions can be compensated by adding one or two other conditions, and the opposite is true. Usually the liquid temperature ranges from about 10. (3 to about 120 t, preferably about 20 ° to about 8 ° C., and more preferably about 25 ° to about 6 ° (rc, which should be suitable for most cases) Use lower or higher temperature. As mentioned above, it has been surprisingly found that the smallest loss of organophosphite ligands occurs in the reaction product fluid containing the metal-organophosphite coordination dislocation catalyst. When in contact with acid scavengers, or in contact with water, and then the contacted water is treated with acid removal substances, even at high temperatures. Generally, this treatment is under pressure ranging from ambient pressure to reaction pressure And the contact time can be changed from seconds or minutes to hours or more. Two ----—- This paper size applies the Zhongguan Standard (CNS) M specification (21 () > < 297 公 # ) (Please read the precautions on the back before filling out this page), 11 509694 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs-75- V. Description of the invention (72) Furthermore, 'in the self-reaction product fluid according to the present invention The success of the removal of tritium acid compounds can be measured by the presence of hydroformylation reaction media. The rate of degradation (consumption) of the organophosphite ligand in the substrate can be measured. This consumption rate can be varied within a wide range, for example, from about g06 to up to about 5 grams per liter per day, and will be subject to coordination It is dominated by the best compromise between body cost and treatment frequency that keeps hydrolysis below the level of autocatalysis. The acid scavenger and water treatment of the present invention are preferably performed in a way that makes it present here The consumption of the desired organic phosphite ligand in the reaction medium is maintained at an acceptable rate, for example, per gram of ligand per liter per day, and more preferably 0.1 gram of ligand per gram per day. , And the best is 0.06 grams of ligand per liter per day. When the phosphate compound is neutralized and extracted in water, the pH of the water will decrease and become more and more acidic. When the water reaches no When the acidity is acceptable, it can be simply replaced with fresh water. The preferred operation method of the present invention is to remove all or part of the reaction product fluid before the aldehyde is removed, or the reaction product after the aldehyde is removed. The fluid concentrate passes through water and passes through The contacted water passes through one or more acid removal material beds. Alternatively, water can be sprayed or otherwise added to at least one reaction zone or at least one separation zone to achieve acidity control. The acidity control can then be applied. The formed water layer is separated from the reaction product fluid, such as decantation. One advantage of this system is that if the acidity is formed in the reaction product fluid, the extraction capacity can be used. The present invention is not intended in any way Limited to allowable devices (whether inside or outside the reaction zone, separation zone, scrubbing zone, or acid removal zone) to contact the reaction product fluid with water or water and acid removal materials . The paper size applies to the Chinese National Standard (CNS) A4 (2i0x297 mm) (please read the notes on the back before filling out this page) Order 509694 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy -76-A7 B7 5 (73) For the purpose of the present invention, "untouched water" is intended to include water that has not been in contact with the reaction product fluid ', and "contacted water" is intended to include already Water in contact with the reaction product fluid and / or acid removal material. Any method of preparing uncontacted water for use with the method of the present invention can be used as long as the water is substantially free of catalyst poisons, inhibitors, or compounds that promote undesirable side reactions in the catalyst solution. For an overview of water treatment technology, see Kirk Othmer, Encyclopedia of Chemical Technology, Fourth Edition, 1996. Water treatment should begin by assessing the water quality requirements of this method. For acid extraction from reaction product fluids containing metal-organophosphite coordination catalysts, the required water quality is usually boiler quality or better. The source of the water for purification can vary greatly in purity, from river water containing roundwood, silt, and other debris to relatively pure water vapor condensate. If river water is to be used, purification begins with filtration of the largest piece. Rhenium or screens can be used for this first filtration step. A variety of techniques are available to remove other solids that may be present in the water, including, • sedimentation, centrifugation, filtration, coagulation, flocculation, magnetic separation, or a combination thereof. After obtaining clear water, the remaining dissolved solids can also be treated in a variety of ways. Distillation is still generally performed. The dissolved salts can be treated with other acids or assays to precipitate certain compounds. The added acid or base is selected based on the solubility of the compound to be made. Ion exchange is another popular method for removing dissolved salts. The most commonly used ion exchange method uses sodium as the cation. Other ion exchange techniques using protons or ions can also be used. Adsorption can be used to remove some metal salts and possible organic compounds. Standard of activated carbon paper is applicable to China National Standard (CNS) A4 (2ί〇 × 297 mm)

V. Description of the invention (74 A7 B7 Printed by the Consumer Cooperative of the Central Standard Bureau of the Ministry of Economic Affairs for use as an adsorbent ° Thin film is another technology that can be used to remove tritium salt or other colloidal particles. The secret is the size, charge, Separation is based on differences in hydrophobicity or other physical-chemical properties. Reverse osmosis is an example of the use of membranes to purify water. Even bismuth is used in cold households ^ J You Ge I. If a decomposing gas such as oxygen is present, water can be separated by Steam steam stripping, or allowing it to be emptied to remove or replace dissolved I gas: a preferred method of purifying the untouched water necessary for acid removal, is a combination of some of the foregoing techniques. Use of additives Internal technology that neutralizes the harmful effects of impurities can also be used to prepare untouched water for extraction, but the external technology described in the previous paragraph is more preferred. Contacted technology that can be used in the present invention Water may include any suitable water such that the range of impotence contacted with water may cover from about 2 to about 12, 2.5 to about 1 bu and more preferably about 3 to about 10. The water passes through the extractor and / Or add water to At least one reaction zone and / or at least one separation zone; the rate m㈣the pH of the water 値 to the desired extent the flow rate of the water extractor 1 can cause ―quantitative- or multiple products to be removed from this process Means the water effluent. In a preferred embodiment of the present invention, the aldehyde product removed or recovered by water extraction can be recovered and returned to the process, as shown in the chart of the taxi chart For example, this—or multiple aldehyde products—may be returned; in the acidification process, in which the water product from the extractor is stripped by steam and the organic phase at the head of the condensing stripper is returned to the hydroformylation process ;. The water phase at the head of the stripper can be returned to the feed of the stripper. The tail of the stripper contains the acidic decomposition products from the catalyst. -77-Wood paper scale suitable for the country ^ quasi (Cn1TaS (210X297 ^ 11 (Please read the notes on the back before filling this page)

1T • -I- -1 i -1 ........ 8 509694 A7 B7 V. Description of the invention (75) Treatment of phosphoric acid compounds containing-removed from the reaction product fluid with-or more acid removal substances The water may be carried out in an appropriate and undesired manner to any desired suitable method or manner of the basic method used to derive the reaction product fluid. For example, this acid removal treatment may be performed on all or any part of the water to be treated and removed from at least one reaction zone. The treated water can then be returned to at least one scrubbing zone. Alternatively, water can be sprayed or otherwise added to at least one reaction zone or at least one separation zone to achieve acidity control. The formed aqueous layer can then be separated from the product fluid, such as by decantation, and treated with one or more acid removal materials to remove phosphoric compounds. The treated water can then be returned to at least one reaction zone or at least one separation zone. Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economics to contact water containing one or more acid-removing substances containing phosphonium acidic compounds removed from the reaction product fluid, and the processing conditions, such as the amount of water and the number of acid-removing substances The type, temperature, pressure, and contact time are not critical and obviously need only be sufficient to achieve the desired result. For example, the treatment can be performed in any suitable vessel or container, which is a suitable device that provides a water supply with sufficient contact with one or more acid-removing substances, and can be used herein. The amount of water and acid removal substance used in the present invention, and the contact time, need only be sufficient to remove at least some amount of phosphoric acid compound that will cause hydrolytic degradation of the desired organic phosphite ligand. The amount of water and acid removal substance is preferably sufficient to maintain at least the concentration of such a phosphoric acid compound, which is lower than the lower limit content that would cause rapid degradation of the organic phosphite ligand. It is also preferred that the portion of water 'which is sent from the scrubbing zone to the acid removal zone can be controlled on the basis of water in the scrubbing zone. -78 (Please read the precautions on the back before filling this page) This paper size is applicable to Chinese National Standard (CNS) A4 specification (21〇Xπ? Public attack) A7 B7 76 V. Description of the invention (丨 ^-衣- (Please read the precautions on the back before filling out this page} Treating the reaction product fluid with one or more acids to remove the substance will not unduly and adversely affect any requirement of the basic method used to derive the reaction product fluid Appropriate method or manner. For example, this acid removal treatment may be performed on all or any part of the reaction product fluid that is to be treated and has been removed from at least one reaction zone or at least one separation zone. Then, it may be Return the treated reaction product fluid to at least one scrubbing zone or at least one separation zone. Alternatively, an acid removal substance, such as calcium carbonate, may be added to at least one reaction zone or at least one separation zone to Achieving acidity control. The precipitate formed can then be removed from at least one reaction zone or at least one separation zone. The acid removal material used is in a fluid containing a self-reaction product. The water in which the phosphoric acid compound is removed should have limited solubility. In the broad implementation of the present invention, the so-called "insolubility" means that it is insoluble at the temperature used in the practice of the present invention. Central standard of the Ministry of Economic Affairs Illustrative examples of acid-removing substances that can be used in the present invention are printed by the Bureau's Consumer Cooperative, including, for example, oxides, hydroxides, carbonates, bicarbonates, and carboxylates of metals. Preferred acid-removing substances include carbonic acid Salts, such as calcium carbonate. The acid-removing substances that can be used in the present invention are not critical and can be effective in removing such phosphoric acid formed in a method catalyzed by metal-organophosphite complexes Compounds, and thus prevent and / or reduce the hydrolytic degradation of the organic phosphinate ligands and the inactivation of the metal-organic phosphite coordination catalysts, which may be the Occurs during the process of the phosphoric acid complex coordination catalyst method. It is preferred that the acid-removing substance has low solubility in water and obtains phosphate. 10x ^^

2. Description of the invention (77 7 also has very low solubility in water. The allowable gold f 'constituting the acid-removing substance includes metals of Groups 2, 11, and 12 and is selected from calcium (Ca), silver (Ag), and zinc (Zn ) Temple. Illustrative examples of metal oxides that can be used in the present invention include, for example, calcium oxide, silver oxide, zinc oxide, etc. Illustrative examples of erbium oxides that can be used in the present invention include, for example, hydroxides, zinc hydroxide, and the like. Can be used in Illustrative examples of the carbonate of the present invention include, for example, calcium carbonate, silver carbonate, zinc carbonate, etc. Illustrative examples of the carboxylates that can be used in the present invention include, for example, calcium 2-ethylhexanoate. Illustrative examples include the permissible acid-removing substances described in the Encyclopedia of Chemical Technology, Fourth Edition, 1996, the relevant parts of which are incorporated herein by reference. As mentioned above, the reaction product fluid may contain at least several amounts of various Phosphoric acid compounds, such as MAT03, uronic acids such as hydroxyalkylphosphonic acid, h3P0, etc., and other acidic compounds, such as carboxylic acids, such as butyric acid, etc. If one or more acids are removed, the substance should become carboxylic acid. Acid saturation, the present invention The method can still be operated at the desired low content of phosphoric acid compounds. The stronger the phosphoric acid compounds can be replaced, the weaker the acids from the acid removal substance in the operation of the present invention are. Printed (please read the notes on the back before filling this page) In the specific embodiment of the present invention, it involves removing at least some amount of scale acidification sufficient to remove one or more scales from the reaction product fluid or salty contact water. Character's acid removal material, introducing at least one reaction zone, at least one separation zone, at least one scrubbing zone, and / or at least one acid removal zone to treat at least a portion of the method derived from the method and which also The reaction product fluid containing the decaying compound formed during the process, the precipitation of any salt in different zones can be removed by filtration or deposited on the carrier, and by mechanical ----------- ----80-This paper size is in accordance with Chinese National Standard (CNS) A4 specifications (21 ^ 1 ^^ 1 ^ 111) --- Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention ( 78) The device is removed. Moreover, for carboxylates, carboxylic acid can be added to different zones and converted on the spot to the carboxylate, or the carboxylate itself can be added directly to the different zones. Removal of acidic compounds from the reaction product fluid or water can be achieved simply by contacting the reaction product fluid or water with one or more acid removal substances. The amount of acid removal substance relative to the reaction product fluid or water is based on phosphoric acid The amount of the chemical compound in the reaction product fluid or water depends on the amount of the acid removal substance, and only needs to be sufficient to reduce the concentration of the phosphoric acid compound to the required number. Based on the reaction product fluid or water standard, the volume of acid removal material is about 0 ml of acid removal material per liter of reaction product fluid or water to be treated. For removal from reaction product fluid or water Phosphoric compounds should already be satisfactory. The contact time between one or more acid-removing substances and the reaction product fluid or water containing a phosphoric acid compound removed from the reaction product fluid need only be sufficient to remove at least some amount of the phosphoric acid compound from the water. The reaction product fluid can be contacted with one or more acid-removing substances in batch or continuous (or semi-continuous) mode with water containing a phosphoric compound. When operating in batch mode, its contact preferably involves removing the reaction product fluid or water containing a phosphate compound with one or more acids to remove the substance; mix for about 0.01 to about 10 hours, more typically about 0.1 to about 5 hours, followed by any known separation technique, such as sedimentation, centrifugation, filtration, or the like. The present invention is preferably implemented in a continuous mode by passing the reaction product fluid or water containing a phosphoric acid compound through one or more beds containing an acid-removing substance, such as solid Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the notes on the back before filling out this page) Order 509694 Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (79) A fixed bed, a moving bed, or a fluidized bed has a liquid flow rate ranging from about 01 to about 100 bed volumes per hour, and more typically from about 1 to about 20 bed volumes per hour. The present invention can be used with any conventional device designed for acid removal, and special designs are not required. Proper contact between one or more acid-removing substances and the reaction product fluid or water containing a phosphoric compound is obviously important to obtain the best results. As will be apparent to those skilled in the art, one or more acid removal material beds are used to remove phosphate compounds from the reaction product fluid or water until the treated reaction leaves the one or more acid removal material beds. The content (concentration) of acidic compounds in the product fluid or water is reduced to the required number. The number of acid-removing material beds that can be used in the present invention is not critical. One or more acid-removing material beds can be used, such as a series of such beds, and any such bed can be easily as needed or desired Way to remove and / or replace. Optionally, organic nitrogen compounds can be added to the reaction product fluid, such as a hydroformylation reaction product fluid, to remove acidic hydrolysis by-products formed during the hydrolysis of the organic phosphite ligand, such as in U.S. Patent 4,567,3. As stated in 6. Such organic nitrogen compounds can be used to react and neutralize acidic compounds by forming a conversion product salt therewith, thereby preventing metals such as germanium from being incompatible with acidic hydrolysis by-products, and therefore when metals (such as germanium) catalysts are reacting (such as beeze) Under the conditions of tritiation, it helps to protect its activity when present in the reaction zone. The choice of organic nitrogen compounds that provide this function is partially indicated by the desire to use basic substances that are soluble in the reaction medium and will not catalyze aldol and other condensations at significant rates Product formation or tendency to react inappropriately with products such as aldehydes. ----— -82- This paper size is applicable to the China Standard (cns) A4 specification (-'~~ ——-(Please read the precautions on the back before filling out this page),?! 509694 Central Ministry of Economic Affairs Kl B7 printed by the Consumer Cooperatives of the Bureau of Standards V. Invention Description (80) ^ ^ This organic nitrogen compound may contain 2 to 30 carbon atoms, and preferably 2 to 24 carbon atoms.-Grade amines should be excluded , Can not be used as the organic nitrogen compound. Preferably the organic nitrogen compound should have a partition coefficient that is favorable for solubility in the organic phase. Generally speaking, a better organic compound that can be used to remove the phosphoric acid compound present in the reaction product fluid of the present invention Nitrogen compounds include those with a pKa 値 within ± 3 of the impotence used in contact with water. In the best case, the pKa 値 of this organic nitrogen compound is approximately the same as the pH 値 of the water used. Of course, the It is clear that although at any one time, in any particular method, it is preferred to use only one such organic nitrogen compound, it is also possible to use a mixture of two or more different organic nitrogen compounds in any particular method if desired Examples of organic nitrogen compounds include trialkylamines such as triethylamine, tri-n-propylamine, tri-n-butylamine, tri-isobutylamine, tri-isopropylamine, and tri-n-hexylamine. , Tri-n-octylamine, dimethyl_isopropylamine, dimethylhexadecylamine, methyl_di-n-octylamine, etc., and it contains one or more non-interfering substituents (such as hydroxyl) Substituted derivatives such as triethanolamine, N · methyl_di_ethanolamine, gins- (3-hydroxypropyl) _amine, etc. Heterocyclic amines can also be used, such as pyridine, methylpyridine, diamine Methylpyridines, trimethyleridine, N-methylhexahydropyridine, N-methylmorpholine, N-2, -ethylmorpholine, p-quinolin, iso-piquine, 4 Lin, acridine, quinine ring, as well as diazines, triazoles, two farming and three p well compounds, etc. It is also suitable and possible users, is aromatic tertiary amines, such as N, N-di Methylaniline, N, N-diethylbenzylamine, N, N-dimethyl-p-toluidine, N-methyldiphenylamine, ν, N-dimethylbenzylamine, N, N- Dimethyl-1-naphthylamine, etc. Compounds containing two or more amine groups--83- Standards are applicable to China National Standard (CNS) A4 specifications (2i0x297 mm) 丨 ^ ϊ ·· ^ clothing-(Please read the precautions on the back before filling out this page), 1T 509694 Staff Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Printing kl-*-a B 7 ^ ^ ^ ----------------------------------------- ------ ---- V. Description of the invention (81), such as N, N, N ,, N, -tetramethylethylenediamine and triethylenediamine (meaning 丨, 4 diazabicyclo幷-[2,2,2] _octane) can also be mentioned. Preferred organic nitrogen compounds that can be used to remove phosphoric compounds present in the reaction product fluid of the present invention are those selected from heterocyclic compounds including diazepine, triturate, dihalf, and dihalf. For example, in the same case as the present case The disclosure and adoption of the co-pending US patent application serial number (23474234) filed on the date of filing, whose disclosure is incorporated herein by reference. For example, benzimidazole and benzimidazole are better candidates for this purpose. Illustrative examples of suitable organic nitrogen compounds include the permissible organic nitrogen compounds described in Encyclopedia of Chemical Technology, Fourth Edition, 1996, and related references are incorporated herein by reference. The amount of organic nitrogen compounds that may be present in the reaction product fluid to remove the phosphoric compounds present in the reaction product fluid of the present invention is typically a concentration sufficient to provide at least about 0.0001 moles of free organic nitrogen compounds per liter of reaction product fluid . In general, the ratio of organic nitrogen compounds to all organic phosphite ligands (whether bound to germanium or present as free organic phosphite) is at least about (U :: [, and better It is at least about 05: i. The upper limit of the amount of organic nitrogen compounds is mainly governed only by economic considerations. The organic nitrogen compound: organic phosphite Morse ratio of at least about 1.1 to Nanda is about 5: 1. For some purposes, it should be sufficient. It should be clear that the organic nitrogen compound used to remove the phosphoric compound need not be the same as the heterocyclic nitrogen compound used to protect the metal catalyst under severe conditions. For example, it exists in products such as acid and vaporizers, as in the serial number of co-pending US patent applications —-_______-84-........ This paper size applies to China Standard (〇 尔) 6 4 specifications (210 \ 297 male 51 '—-------- (Please read the precautions on the back before filling out this page) &gt; equipment_ 509694 A.7 V. Description of the invention ( 82) Regarding those stated above, however, if the organic nitrogen compound and the The cyclic nitrogen compounds are the same, and perform these two functions in a specific method, then care should be taken to understand that a sufficient amount of heterocyclic nitrogen compounds are present in the reaction medium 'and that this amount of free-state heterocyclic nitrogen compounds is also provided In this method, for example, a vaporizer-separator for hydroformylation, which will allow the two desired functions to be achieved. Therefore, the water will not only be a reaction product containing a metal-organophosphite coordination dislocation catalyst The free-state phosphoric acidic compound is removed from the fluid, and the water is surprisingly #removed from the acidic substance of the conversion product salt, which is formed when an organic nitrogen compound scavenger is used, meaning that the phosphoric acid of the conversion product salt is still It remains in the water, and the processed reaction product fluid, along with the reactivated (free you) organic nitrogen compounds, returns to the reaction zone. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 丨 «---- ( Please read the notes on the back before filling in this page; &gt; When using these methods, such as continuous liquid catalyst recycling hydrogen methylation method, organic polyphosphite coordination is used Another problem has been found when metal catalysts promoted by the catalyst are used. This method involves severe conditions, such as the recovery of aldehydes via a vaporizer-separator, which means that the catalyst ’s catalytic activity is slowly lost. This severe condition exists, for example, in a vaporizer used for the separation and recovery of aldehyde products from their reaction product fluids. For example, 'It has been found that when an organic polyphosphite promoted germanium catalyst is placed under severe conditions, For example, under high temperature and low carbon monoxide partial pressure, the catalyst will inactivate at an accelerated pace over time. It is most likely due to the formation of inactive or less reactive germanium species. It is exposed to such severe conditions for a long time. It may also be easy and redundant. This evidence is also considered to be active catalysts under hydroformylation conditions = germanium-containing complexes, organic polyphosphites, carbon oxides and hydrogen. II I paper scale applies to China National Cloud Standard (0 milk) 8 4 specifications (21〇 \ 97 mm) * 5. Description of the invention (83 A7 B7 copies ^ / During the severe conditions encountered, at least-part allocation Position <―View of carbon oxide ligand They are consistent in that they provide a way to generate catastrophic: non-sexual or less active species. The device for preventing or minimizing the use of such catalysts and / or sinkers is an invention involving co-pending U.S. patent application serial number om.d regarding the above contents and guidance, It includes performing a hydroformylation method in the presence of a free state heterocyclic nitrogen compound of 7F under the conditions of low carbon monoxide partial pressure. Printed by the Consumer Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs. By further explanation, the free-form heterocyclic nitrogen compound is believed to be a substitute ligand for known off-site carbon oxide ligands. # Is a neutral intermediate metal species that is formed during such severe conditions such as vaporization separation It contains metal complexes, organic polyphosphites, heterocyclic nitrogen compounds and hydrogen, thus preventing or minimizing the formation of any such catalytically inactive or less reactive metal species. The further theory is that the maintenance of catalytic activity, or the minimization of its deactivation, throughout the continuous liquid recirculation hydroformylation process is due to the fact that the active catalyst is involved in the particular hydroformylation process involved In the reactor (meaning the hydroformylation reaction zone), it is caused by the regeneration of the neutral intermediate metal species. Xianxin's active catalyst complex containing metals (such as germanium), organic polyphosphite carbon monoxide, and hydrogen under the conditions of high synthesis pressure hydroformylation in the reactor is due to the presence in the reactant synthesis gas One of the carbon monoxide is replaced by the recycled neutral intermediate germanium species foot heterocyclic nitrogen ligand. In other words, carbon oxide, which has a strong ligand affinity for rhodium, will replace the weakly bound heterocyclic nitrogen coordination of the recycled neutral intermediate germanium species formed during the above-mentioned vaporization separation -86-(please first Read the notes on the reverse side and fill out this page) This paper size applies to China National Standard (CNS) Α4 specification (2ί297 × 297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 509694 A7 -------- -B7 V. Description of the invention (84) body, then active catalyst is formed in the hydroformylation reactor. Therefore, due to the possibility of inactivation of the metal catalyst due to such severe conditions, the reaction of the self-containing metal-organic polyphosphite catalyst is carried out in the presence of an additional free-state heterocyclic nitrogen compound. The desired fluid is evaporated or minimized in the product fluid, and the additional compound has a five- or six-membered heterocyclic ring, containing 2 to 5 carbon atoms and 2 to 3 nitrogen atoms, and at least one of the nitrogen atoms contains a double bond . Such free-state heterocyclic nitrogen compounds can be selected from the group consisting of diazoles, triazoles, second crops, and third crops, such as benzimidazole or benzamidine. As used herein, the term "free state", when applied to the heterocyclic nitrogen compound, excludes any acid salts of such heterocyclic nitrogen compounds, that is, by any phosphate compounds present in the reaction product fluid Salt compounds formed by reaction with such free-state heterocyclic nitrogen compounds as discussed above. It should be understood that although it is preferred to use only one free-state heterocyclic nitrogen compound at any one time in any particular method, two or more different ones may be used in any particular method if desired. A mixture of free state heterocyclic nitrogen compounds. Furthermore, during severe conditions, such as during the vaporization process, the amount of such free-state heterocyclic nitrogen compounds present is only required to be the minimum necessary to provide a basis for minimizing at least a portion of this catalyst inactivation f, for example, found under substantially the same conditions in the absence of any free-state heterocyclic nitrogen compound during the vaporization separation of the aldehyde product due to the same metal-catalyzed &lt; liquid recirculation hydroformylation method. The content of such free-state heterocyclic nitrogen compounds ranges from about 0.001 to as high as about 10 weight percent, or higher when needed, so that the total weight of the reaction product fluid to be distilled ------- -~ —— ______- 87-This paper size is applicable to t @National Standards (CNS) A4 regulations; ---- (Please read the precautions on the back before filling out this page) Poly, 11 509694 A7 B7 Central Bureau of Standards, Ministry of Economic Affairs Printed by the Employee Consumption Cooperative 5. The quantity of invention description (85) is the benchmark, which should be sufficient for most purposes. «An alternative method for transferring the acidity of the reaction product fluid to the water content is through the use of heterocyclic amines in the middle, which have sufficient fluorocarbon or siloxane side chains that are immiscible in both the reaction product fluid and the water content Among those. The heterocyclic amine may be first contacted with the reaction product fluid, and the acidity present in the reaction product fluid will be transferred to the nitrogen of the heterocyclic amine. This heterocyclic amine layer can then be decanted or otherwise separated from the reaction product fluid before contacting it with the aqueous portion, where it will once again exist in individual phases. The heterocyclic amine layer can then be returned to contact the reaction product fluid. For the purposes of the present invention, the term &quot; hydrocarbon &quot; is intended to include all permissible compounds having at least one hydrogen and one carbon atom. Such permissible compounds may also have one or more heteroatoms. In a broad sense, Permissible hydrocarbons include acyclic (with or without heteroatoms) and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic organic compounds, which may be substituted or unsubstituted Substitution. The term &quot; substituted &quot; as used herein is intended to include all permissible substituents of organic compounds, unless stated otherwise. In a broad sense, this permissible substituent includes the noncyclic ring of organic compounds. Shaped and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents. Examples of substituents include alkyl, alkoxy, aryl, aryloxy, Hydroxyl, hydroxyalkyl, amine, amine alkyl, halogen, etc., wherein the carbon number may range from i to about 20, or more preferably from 1 to about 12. For suitable organic compounds, the allowable substituents may be One or more, and they are the same or different. It is not intended to be limited in any way by the permissible substituents of organic compounds. --- -88- This paper size applies Chinese national standards (~ ---- 一 ~-I ------ «--- ^ • Approval-(Please read the notes on the back before filling out this page) Order · 509694 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (86) Provide some of the following examples to further Illustrate the invention. Example 1 Use calcium carbonate on alumina to remove hydroxypentylphosphonic acid from water. Pump 130 parts of hydroxypentylphosphonic acid solution per million parts in a stainless steel container and cover the alumina bed 5% calcium carbonate. The flow rate of the acid solution is 0.31 g solution / g CaC03 on the support. These conditions are maintained for two weeks. The pH of the acid solution entering the acid removal bed is 3.2. Water flows out The pH range of the substance is between 9.2 and 11.3, and most of the readings are between 10.5 and 11.0. The concentration of phosphorus and calcium is measured by the induction coupling plasma technology. The concentration of phosphorus and calcium in the inlet acid solution Individual weight ratios are 24 ppm and less than 1 ppm. The concentration of squat and # 5 in the effluent is individually low. 1.1 parts per million and 70 parts by weight per million parts. After two weeks of operation at (0.31 g solution) / (g CaC03 and support), the flow rate of the acid feed solution was increased. To (0.93 g solution) / (g CaC03 and support). The pH of the water effluent has decreased to 10.1 and has continued to stabilize to 8.65 over the next 9 days. Example 2 This comparative example illustrates ligand F (As confirmed herein) in a butyraldehyde solution containing 200 parts of germanium and 0.39% by weight of ligand F per million parts in a butyraldehyde solution containing aldehyde dimers and trimers, in addition to an acid or benzo Stability in the absence of imidazole. In a clean, anhydrous 25 ml vial, add 12 g of the butyraldehyde solution. After 24 and 72 hours, the sample was analyzed for ligand F using high performance liquid chromatography. The weight percentage of ligand F was determined by high performance liquid chromatography relative to a calibration curve. After 24 or 72 hours, no concentration of ligand f was found ------- ** · pack-(Please read the precautions on the back before filling this page) Order

509694 A7 B7 V. Description of the invention (87-degree change. Example 3 This example is similar to Example 2, except that phosphoric acid was added to simulate the type of acid that may be formed during the hydrolysis of the organic phosphite. The procedure of Example 2 was repeated, but modified 0.017 g of phosphorous acid (H3P〇3) was added to a solution of 12 g. After 24 hours, the concentration of ligand F had decreased from 0.39 to 0.12% by weight; after 72 hours, the concentration of ligand F It has been reduced to 0.004% by weight. This data shows that strong acid will catalyze the decomposition of ligand F. Example 4 This example is similar to Example 2, except that phosphoric acid and benzamidine are added. The procedure of Example 2 was repeated, but the modification was Add 0.018 g of sub-transacid and 0.0337 g of benzimidazole to the solution. After 24 or 72 hours, no decomposition of ligand F was found. This shows that the addition of benzimidazole effectively buffers the effect of strong acids and thereby Prevent rapid decomposition of ligand F. Example t The following series of experiments were performed to determine the relationship of the effectiveness of the base PKa 値 to the retention of the base in the organic phase when contacted with an aqueous solution of isomolar acid. Ministry of Economic Affairs Printed by the Consumer Standards Cooperative of the Central Bureau of Standards (Please read the notes on the back before filling this page.) In all cases, experiments are performed under nitrogen, unless otherwise specified. Solutions are prepared by placing -amount of acid or solvent in the solvent so that The final concentration is equal to mol / liter. By using a W mol / liter solution and diluting to the specified concentration, ΐχΐ〇_3 mol / liter liquid is prepared. Ear / liter, 'Moxibustion Tianji / Kailing Defect', you prepare a 1x10_5 mole / liter solution in the same way, and the correction is 丨 3 ^ jin ”parts 1 X 1 (Γ 3 mole / liter solution, instead of 0.1 mole / liter Liter of solution.

509694 A7 B7 V. Description of the invention (88

In each extraction experiment, 5 ml of a solution in butyric acid was added to a dry, dry vial. In this vial, 5 ml of iso-Mormon PO3 solution was added. The resulting mixture was quickly shaken for several minutes and then the phases were allowed to separate. Then, transfer 1 ml of the aqueous layer to a clean, dry, broken bottle. In this vial, 1 ml of sodium / potassium phosphate buffer at pH 値 7 and 0.1 liter of Tergitol 界面 15-S-9 surfactant were added. The solution was shaken vigorously, and the alkali content of one liquid was analyzed by high performance liquid chromatography. Then 'compare this test with the digas solution at the initial concentration. The calculated distribution coefficient is the distribution of the alkali from the organic phase to the aqueous phase, and is defined as the amount tested in the aqueous phase / the amount of alkali in the organic phase. The results of the extraction experiments are summarized in Table A. Table A (Please read the precautions on the back before filling out this page) --- ^ _ 装-pKa 値 concentration (Moore / liter) printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 1 2-Hanji ρ ratio lake 5.1 1 X 10_3 2 2-segment ρ ratio lake 5.1 1 X 10'5 3 Koulin 4.8 1χ1 (Γ3 4 4.8 1 X 10'5 5 3-ethyl ρ ratio lake 3.3 1 X 10'3 6 3-Ethyl-pyridine 3.3 1 X 10'5 7 Phenylpyrene 1.6 1 X 10'3 8 Benzotripyrene 1.6 1 X 10 &quot; 5 9 1-Feyl-2_tetrahydrop-pyrrolidone -0.7 1 X 10 · 3 10 1-benzyl-2-tetrahydroerone-0.7 lxl (T5 — ^ Agronomy (mol / liter) η3ρο3 1 x ΙΟ'3 0.22 η3ρο3 1 X ΙΟ'5 0.30 η3ρ 〇3 1 X ΙΟ'3 0.43 η3ρο3 1 χ ΐ〇_5 1.20 η3ρο3 1 χ ίο-3 0.93 η3ρ〇3 1 χ ΐ〇 ~ 5 0.00 η3ρο3 ι χ ίο-3 0.08 η3ρο3 ι χ ι〇 &quot; 5 0.00 Η3Ρ 〇3 ι χ ι〇 &quot; 3 0.02 Η3ΡΟ3! Χΐ0'5 ^ — 0.00 μ — μ%, the more the alkali is. Although the present invention has been illustrated by some of the foregoing examples, it should not be interpreted as being -91-this paper Scale

1T 509694 A7 B7 V. Description of the invention (89) Its limitations; instead, the invention covers the general field as disclosed above. Various amendments and specific implementation can be implemented without departing from its spirit and fan garden (please read the precautions on the back before filling this page) _ 装-

、 1T Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) A4 (2i0X297 mm)

Claims (1)

509694 A8 B8 C8 D8 Patent Application Scope 1. A reaction product fluid containing one or more phosphoric compounds, metal-organic phosphite coordination catalysts, and optionally a free-state organic phosphite ligand Method of separating the one or more scale acidic compounds 'This method includes (a) treating the reaction product fluid with water sufficient to remove at least some amount of the one or more phosphoric acid compound from the reaction product fluid' and (b) The water containing the phosphorous compound removed from the reaction product fluid is treated with an acid removal substance sufficient to remove at least some amount of the one or more phosphoric compounds from the water. 2. · A stabilization method to make the organic phosphite ligand resistant to hydrolytic degradation and / or metal-organophosphite coordination mismatch catalysts to resist inactivation 'This method includes (a) the use of sufficient self-reaction Remove at least some amount of water of one or more phosphoric acid compounds from the product fluid, and treat the free-state organic subscale ligands containing metal-organic phosphite coordination catalysts and optionally the ligand and also contain The reaction product / dead body of one or more of the acidic compounds and (b) water containing the phosphoric acid compound removed from the reaction product fluid, using at least some amount of the one or more phosphoric acid from the water Compound acid removal material treatment. 3. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) A method to prevent and / or reduce the hydrolytic degradation of organic phosphite ligands and / or metal-organic phosphorous acid Method for deactivating an ester coordination catalyst, this method includes (a) treating water containing a metal-organic phosphite compound with water sufficient to remove at least some amount of one or more phosphoric compounds from a reaction product fluid Dislocation catalysts and optionally selected free-state organophosphite ligands that also contain one or more reaction product fluids of an acidic compound, and (b) containing the reaction product fluid removed from the reaction product fluid- 93 This paper size applies to Chinese National Standard (CNS) A4 specifications (21〇 &lt; 297 mm) 509694 A8 B8 C8 D8 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 6. Application scope of patents: water of acidic compounds, Treat with an acid removal substance sufficient to remove at least several amounts of the one or more squamous compounds from the water. 4. An improved method comprising reacting one or more reactants in the presence of a metal-organic phosphite coordination catalyst and optionally a free-state organic phosphinic acid g ligand Reaction product fluids containing one or more products. Improvements include preventing and / or reducing the hydrolytic degradation of organophosphite ligands, and the inactivation of metal-organophosphite coordination dislocation catalysts, which This is done by using one or more acid-removing substances sufficient to remove at least a number of phosphoric compounds from the reaction product fluid, treating at least a portion of the reaction derived from the process and also containing phosphoric compounds formed during the process Product fluid. 5. An improved method according to item 4 of the patent application park, which includes ① in at least one reaction zone, a metal-organic phosphite coordination dislocation catalyst and a free-state organic phosphine selected as appropriate Reacting one or more reactants in the presence of a ligand to produce a reaction product fluid comprising one or more products, and (ii) in the at least one separation zone or in the at least one reaction zone, from the reaction The product fluid separates one or more products, and improvements include preventing and / or reducing the hydrolytic degradation of any of the organic phosphite ligands and the inactivation of the metal-organic phosphite coordination catalysts. This is done by (a) treating, in at least one scrubbing zone, at least a portion of the phosphate compound from the reaction product fluid with at least a portion of the water, and treating at least a portion derived from the process and also containing formation during the process The reaction product fluid of scale acidic compounds, and (b) in-at least one acid removal zone, contains at least a part of the reaction product -94- This paper size applies Chinese National Standard (CNS) A4 Grid (210X297mm) '' ~ '(Please read the precautions on the back before filling this page) Ur Pack · 、? Τ 509694 A8 B8 C8 D8 VI. Water for phosphate compounds removed from the fluids for patent application And treated with an acid-removing substance sufficient to remove at least some amount of a phosphoric compound from the water. (Please read the notes on the back before filling out this page) 6. The improvement method according to item 4 of the scope of patent application, which includes ④ in at least one reaction zone, the metal-organic phosphite coordination dislocation contact Reacting one or more reactants in the presence of a solvent and optionally a free-form organic phosphite ligand to produce a reaction product fluid containing one or more products, and (ii) in at least one separation zone or In the at least one reaction zone, one or more products are separated from the reaction product fluid, and improvements include preventing and / or reducing any hydrolytic degradation of the organic phosphite ligand and the metal-organic phosphite Deactivation of the coordination mismatch catalyst by (a) using at least one acid removal zone in at least one acid removal zone sufficient to remove one or more acid removal materials from the reaction product fluid Processing at least a portion of the reaction product fluid derived from the method and also containing phosphoric compounds formed during the method, (b) returning the processed reaction product fluid to the at least one The reaction zone or the at least one separation zone. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 7. The improved method according to item 4 of the patent application park, which includes ① in at least one reaction zone, a metal and organic phosphite coordination catalyst and video In the presence of a free-state organic phosphite ligand, one or more reactants are reacted to produce a reaction product fluid containing one or more products, and the rhenium is in at least one separation zone or in the at least one reaction In the zone, one or more products are separated from the reaction product fluid, and improvements include preventing and / or reducing any hydrolytic degradation of the organic phosphite ligand and the metal-organophosphite coordination mismatch -95- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 509694 A8 B8 C8 D8 VI. Inactivation of Patent Application Media Yes, in at least one scrubbing zone, treat at least one portion of the derivative with water sufficient to remove at least some amount of phosphoric acid compound from the reaction product fluid The method also contains a reaction product fluid of a phosphoric compound formed during the method, so that the processed reaction product fluid is returned to the at least one reaction zone or the at least one separation zone, (C) at least one acid shift In the removal zone, one or more acid-removing substances sufficient to remove at least several amounts of the phosphoric acid compound from the water, treating at least a portion of the water containing the phosphoric acid compound removed from the reaction product fluid, and The treated water is returned to the at least one scrubbing zone. 8. An improved method according to item 4 of the scope of patent application, which includes ① in at least one reaction zone, metal-organophosphite coordination dislocation catalyst and optionally free-form organic phosphite coordination Reacting one or more reactants in the presence of a solid to produce a reaction product fluid comprising one or more products 'and (ii) in at least one separation zone or in the at least one reaction zone' from the reaction product fluid Isolation of one or more products, the improvement of which includes preventing and / or reducing any hydrolytic degradation of the organic phosphite ligand and inactivation of the metal-organophosphite coordination catalyst, by取出 taking at least a portion of the reaction zone or the at least one separation zone, at least a portion of the reaction product fluid derived from the process and also containing phosphoric compounds formed during the process, (b) at least one acid shift In the removal zone, one or more acid-removing substances sufficient to remove at least some amount of phosphoric acid compound from the reaction product fluid are treated, and at least a portion of the process is derived from the method and also contains There are __ -96 -____ Paper sizes suitable for Laijia County (CNS) A4 specifications (21GX297 mm 1 (please read the precautions on the back before filling this page) Printed by the cooperative 509694 A8 B8 C8 D8 VI. The reaction product fluid of the phosphoric acid compound formed during the application of the patent application method, and the processed reaction product fluid is returned to the at least one reaction zone or the at least one separation zone And, (d) replace the one or more acid removing substances as appropriate. 9. The improved method according to item 4 of the scope of the patent application, which includes (i) in at least one reaction zone, in a metal-organic phosphite Reacting one or more reactants in the presence of a coordination mismatch catalyst and optionally a free-state organic phosphite ligand to produce a reaction product fluid containing one or more products, and (ii) at least one In the separation zone or in the at least one reaction zone, one or more products are separated from the reaction product fluid, and improvements include preventing and / or reducing any of the organic metagenous acids Hydrolytic degradation of the ester ligand and deactivation of the metal-organophosphite coordination dislocation catalyst are performed by (a) removing at least one of the at least one reaction zone or the at least one separation zone A portion of the reaction product fluid derived from the process and also containing phosphoric compounds formed during the process, (b) in at least one scrubbing zone, using at least a sufficient amount of phosphoric acid to be removed from the reaction product fluid Compound water, treating at least a portion of the removed reaction product fluid derived from the process and also containing phosphoric compounds formed during the process, (c) returning the treated reaction product fluid to the at least one reaction zone or The at least one separation zone, (d) taking out at least a portion of the water containing the phosphoric acid compound removed from the reaction product fluid from the at least one scrubbing zone, (e) at least one acid shift In the removal zone, use one or more acid-removing substances sufficient to remove at least some amount of transacidic compounds from the water, and treat at least ___ See 97 pages This paper applies Chinese standards (CNS) A4 specification (210X297 mm) '(Please read the precautions on the back before filling this page). Equipment, tT i Printed by 509694 A8 B8 C8 D8 points of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, Patent Support A portion of the extracted water containing phosphoric acid compounds removed from the reaction product fluid, (f) returning the treated water to the at least one scrubbing zone, and (g) replacing the one or more as appropriate Acid removes substance. 10. An improved method according to item 4 of the scope of patent application, which includes (i) in at least one reaction zone, a metal-organic phosphite coordination dislocation catalyst and optionally a free organic arsonite Reacting one or more reactants in the presence of an ester ligand to produce a reaction product fluid comprising one or more products, and (ii) in at least one separation zone or in the at least one reaction zone, from the The reaction product fluid separates one or more products, and improvements include preventing and / or reducing the hydrolytic degradation of any of the organic sulfinate ligands and the loss of the metal-organic sulfinate coordination dislocation catalyst. Live action by introducing into the at least one reaction zone and / or the at least one separation zone enough to remove at least some amount of one or more acid-removing substances of phosphoric acid compounds from the reaction product fluid, treating At least a portion of the reaction product fluid is derived from the process and also contains phosphoric compounds formed during the process. 11. An improved method according to item 4 of the scope of patent application, which includes ① in at least one reaction zone, a metal-organic imidate coordination catalyst and a free-form organic phosphite compound selected as appropriate Reacting one or more reactants in the presence of a site to produce a reaction product fluid comprising one or more products, and separating from the reaction product fluid in at least one separation zone or in the at least one reaction zone One or more products, the improvement of which includes preventing and / or reducing any hydrolytic degradation of the organic phosphite ligand and the metal-organophosphite coordination mismatch contact -98-This paper is applicable to China Standard (CNS) A4 specification (21GX 297 mm) '~ side-(Please read the precautions on the back before filling out this page) Binding, ordering · Printed by the Central Consumers Bureau of the Ministry of Economic Affairs Consumer Cooperatives 509694 A8 B8 C8 D8 5, Patent application scope &quot; ~ ^ ~ 'The inactivation effect of the medium is to introduce the water sufficient to remove at least some amount of phosphoric acid compound from the reaction product fluid to the at least one reaction zone. And / or in the at least one separation zone, treating at least a portion of a reaction product fluid derived from the method and also containing a phosphoric compound formed during the method, and osmium in at least one acid removal zone, At least a portion of the water containing the phosphoric acid compound removed from the reaction product fluid is treated with an acid removal substance sufficient to remove at least some amount of the phosphoric acid compound from the water. 12. An improved method according to item 4 of the scope of patent application, which includes ① in at least one reaction zone, a metal-organic phosphite coordination catalyst and a free-state organic phosphite compound selected as appropriate Reacting one or more reactants in the presence of a site to produce a reaction product fluid comprising one or more products, and (ii) in the at least one separation zone or in the at least one reaction zone, from the reaction product Fluid separation of one or more products, the improvement of which includes preventing and / or reducing any hydrolytic degradation of the organic phosphinate ligand and the inactivation of the metal-organic phosphinate coordination catalyst, This is done by (a) taking at least a portion of the reaction product fluid derived from the process and also containing phosphoric compounds formed during the process from the at least one reaction zone or the at least one separation zone, (b) In at least one scrubbing zone, use at least enough water to remove at least a thousand phosphate compounds from the reaction product fluid, treating at least a portion of the process derived from the process and also containing After taking out the reaction product fluid of the phosphoric acid compound, (c) returning the processed reaction product fluid to the at least one reaction zone or the at least one separation zone -99- This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the notes on the reverse side before filling out this page) Binding and binding 'i Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 509694 A8? 8s ___D8 6. Scope of patent application ~ surface ~-belt, (D) in at least one scrubbing zone, use water containing phosphoric acid compounds removed from the reaction product fluid, using one or more acid removal substances sufficient to remove at least some amount of phosphoric acid compounds from the water Processing, and (e) optionally replacing the one or more acid-removing substances. 13. The method according to the scope of application for patents 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, including hydroformylation, hydrogenation (intramolecular and molecular Method), hydrocyanation, hydrofluorination, hydrazone esterification, amination, alcoholysis, carbonylation, isomerization or transfer hydrogenation. 14. The method according to item i, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 of the scope of the patent application, wherein the acid-removing substance is selected from items 2, 11, and 12 Group metal oxides, hydroxides, carbonates, bicarbonates and carboxylates. 15. A method according to item j, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, in which the reaction product fluid contains a homogeneous or heterogeneous metal-organic sublayer Phosphate coordination catalysts, or at least a portion of the Wei reaction product stream system, contacts the fixed heterogeneous metal-organic phosphite coordination catalysts during the process. 16. The method according to item 5, 6, 7, 8, 9, 10, ^, or η of the patent application park, wherein the separation of one or more products from the reaction product fluid is derived from the treatment of at least part of the water with This method also contains before or after the reaction product fluid of the phosphoric acid compound formed during the method. 17 According to the scope of application for patents 1, 2, 3, 4, 5, 6, 7, 8, Q --- -卜 丨 -10 装 丨 — (Please read the precautions on the back before filling this page) Order_ Six 509694 A8 B8 C8 ___ D8, the method of applying for patent scope 10, 11 or 12, wherein the metal-organophosphite coordination dislocation catalyst comprises a complex that is mismatched with the organic phosphite ligand, and The position system is selected from: (i) a monoorganic phosphite represented by the formula: R—O—P, 〇 / wherein R1 represents a substituted or unsubstituted trivalent hydrocarbon group containing 4 to 40 carbon atoms or more ⑻ 二 Organic phosphites represented by the following formula: 0 (please read the precautions on the reverse side before filling out this page). · 〇 / P-0-W 、?! Where R2 represents 4 to 40 carbon atoms or More substituted or unsubstituted divalent hydrocarbon groups, and W represents a substituted or unsubstituted monovalent hydrocarbon group containing 1 to 18 carbon atoms or more; (iii) a triorganoarsinic acid represented by the following formula Ester ·· / OR6 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs pOR6 OR6 where each R6 is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon group; and (iv) contains two or more An organic polyphosphite having a tertiary (triple compensation) scale atom and represented by the following formula: 101- 9 · 1 Printed by the Consumer Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs 20. The scope of application for patents is A8 B8 C8 D8 7 / 〇 \ RLO R \ 〇 / a O 'X b A substituted or unsubstituted 'hydrocarbon bridging group' where each R7 is the same or different and represents a divalent hydrocarbon group containing 4 to 40 carbon atoms, each R8 is the same or different and represents 1 to 24 A substituted or unsubstituted monovalent hydrocarbon group of one carbon atom, a and b may be the same or different, and each has a number from 0 to 6, with the proviso that the sum of a + b is 2 to 6, and η is equal to a + b. According to the method of the scope of application for patents j, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, the acidic compounds present in the reaction product fluid are also present in The organic nitrogen compounds in the reaction medium are removed, and at least some of the phosphoric acid compounds in the conversion products reacted between the ammonium acidic compound and the organic nitrogen compound are also removed by water treatment. The method according to item i8 of the scope of patent application, wherein the organic nitrogen compound is selected from the group consisting of diazoles, triazoles, two-tillage and three-tillage. The method according to item 19 of the scope of patent application, in which the organic nitrogen compound is benzene 幷 miso or benzene 幷 竣 -102- Reapply the Chinese National Standard (CNS) A4 specification (210X297 mm) Pack 11 (Please read first (Notes on the back then fill out this page)