The allocation method of the catalyst based on palladium
(57) Abstract:The invention concerns a catalyst based on palladium from the environment, resulting from the reaction of hydroxycarbonate butadiene in partenavia acid. The invention consists in the method of allocating at least part of palladium dissolved in a solution also containing at least 3-pontenova acid, while the above solution is acidified and mixed with an aqueous solution of hydrochloric acid, get two liquid phases, of which the aqueous phase contains at least part of palladium. The technical result - the allocation of at least part of the palladium catalyst dissolved in the processing environment in the form of an ORGANOMETALLIC complex in order to be able to recycle this palladium catalyst in a new reaction hydroxycarbonylmethyl butadiene. 16 C.p. f-crystals, 2 tab. The invention concerns a catalyst based on palladium from the environment in which it is dissolved.More specifically, the invention concerns a catalyst based on palladium from the environment, resulting from the reaction of hydroxycarbonate butadiene to pentano the Asti palladium catalyst, dissolved in the processing environment in the form of an ORGANOMETALLIC complex in order to be able to recycle this palladium catalyst in a new reaction hydroxycarbonylmethyl butadiene.The second method is the implementation of the allocation of at least part pentenoic acids present in the environment.Hydroxycarbonylmethyl butadiene and/or its derivatives, such as, in particular, butanol allyl type, such as 3-butene-2-ol, 2-butene-1-ol, and mixtures thereof, addition products of hydrogen chloride to butadiene (chlorobutane), the main of which is Cotillard, can be carried out using water and carbon monoxide at a pressure above atmospheric pressure and in the presence of a palladium catalyst, soluble in the reaction medium.You can refer to, for example, in European patent application 0648731, in which is given a more detailed description of this technique, although the present invention is not limited to the treatment of the reaction mixtures formed in the process according to this patent application.In U.S. patent application 3857895 described by way of hydroformylation of olefin with what andom, containing at least one aminoalkyl or amidinophenoxy, or aminoaniline, or amidinophenoxy group associated with the trivalent atom of arsenic, antimony or phosphorus.The mixture resulting from the reaction, is treated to separate product hydroformylation and the residue containing the catalyst, the above residue is treated with an acidic aqueous solution to dissolve the catalyst, and the resulting acidic solution is separated.In this method, the ligand reacts with the acid, with the formation of ammonium salts, soluble in acid solution.The reaction mixture used in the method according to the invention, contain more or less significant number of compounds involved in the reaction of hydroxycarbonate, and compounds resulting from the reaction.In addition to the palladium catalyst, which may exist in different chemical forms, the reaction mixture formed contains partenavia acid, in particular 3-pontenova acid, water, hydrochloric acid, and common side reaction products, such as butenes or valeric acid, dicarboxylic acids such as adipic acid is ritel, which can be used in the reaction.The invention relates, therefore, allocation method, at least part of palladium dissolved in a solution also containing at least 3-pontenova acid, which consists in the fact that the above-mentioned solution is acidified and mixed with an aqueous solution of hydrochloric acid to obtain two liquid phases, of which the aqueous phase contains at least part of palladium.When the treated solution comes directly from the stage of hydroxycarbonate butadiene, before acidification, obviously, you have to reset the pressure of carbon monoxide.Used hydrochloric acid usually contains 5 to 40 wt.% hydrochloric acid based on the weight of the solution.Typically, a solution of hydrochloric acid added at the rate of 0.1 to 2-fold volume to the volume of the treated solution.The formation of two liquid phases upon acidification can result from simply adding an aqueous solution of hydrochloric acid, depending on the composition of the treated solution.Do so, in particular, but not exclusively, when the treated solution contains a solvent, mostly not smachivayasi, chlorinated aliphatic or chlorinated cycloaliphatic hydrocarbon.The separation into two liquid phases can also be implemented by adding an organic solvent that is not miscible with water. This addition can be carried out after acidification, at the time of acidification or, if necessary, before acidification.Presence is not miscible with water and organic solvent extraction allows to obtain at least part pentenoic acids present in the treated solution.The temperature at which the processed acidified solution really is not critical to the method. So that you can work in the range 0 - 230oC (the temperature at which it can be held above reaction hydroxycarbonylmethyl). Almost the same work in the range of 20 - 200oC, preferably 40 to 110oC.Acidification with hydrochloric acid allows you to turn palladium present in the treated solution in the form of an ORGANOMETALLIC complex compounds, in tetrachloropalladate acid (H2[PdCl4]). The temperature at which work affects the rate specified pre is no danger to cause precipitation of part of palladium.The organic solvent used for extraction, chosen mainly from an aromatic, aliphatic or cycloaliphatic hydrocarbons, chlorinated aromatics, chlorinated aliphatic or chlorinated cycloaliphatic hydrocarbons, liquid under the operating conditions and, mainly, not miscible with water.For convenience, use an organic solvent having a boiling point below the boiling point 3-pentenol acid.As examples of these solvents, not limiting the scope of protection of the invention include benzene, toluene, xylenes, chlorobenzene, cyclohexane, butadiene, butenes, alkanes, such as hexane, heptane, octane, nonanes, decanes, undecane, dodecane and various mixtures of several of these solvents.The mixture obtained after acidification of the treated solution, and, in some cases, after adding an organic solvent, and mixing, decanted at rest on the organic and aqueous phase.As acidification, extraction with an organic solvent can be carried out at 0 - 230oC, more frequencies between 20 - 200oC and preferably 40 to 110o
Into the flask under stirring with a magnetic stirrer consistently give: 67 mg PdCl2; 360 mg of 37% HCl; 8 g 3-pentenol acid (P3), 9 g of 2-methylglutaric acid; 3 g 2-adelantarnos acid.Then add 20 ml of 10% aqueous HCl solution and 20 ml of organic solvent (specified in table 1, below). The flask contents are stirred at room temperature for 30 minutes By decanting divided into two phases and determine the amount of palladium in these two phases. In all cases, do not see the sediment. The results of the quantitative definitions are collected in table 1.EXAMPLES 4-7
Into the flask under stirring magnetic IU the world acid and 3 g of 2-adelantarnos acid.To obtain a homogeneous solution, the flask content was adjusted to 50oC, then return to the temperature ToC.Then add 20 g of an aqueous solution of HCl (percent concentration (%) HCl are shown in table 2) and 20 g of toluene.After mixing, the duration of which varies according to the examples, the two phases are separated by decantation. Palladium, as well as organic products, quantify in two phases.The distribution coefficients of various products (mass relations factions water layer/organic layer) are summarized in table 2.EXAMPLE 8
Repeat example 6, additionally passing through the mixture bubble for bubble 83 mmol of butadiene, during the extraction.Get the following distribution coefficients: Pd = 36, P3= 0,13 of decollate = 0,9.EXAMPLE 9
In a flask with a volume of 250 ml consistently load 1,668 g (9.4 mmol or 1 g Pd)PdCl2, 54,08 g of 37% aqueous HCl solution, 4,07 g 3-pentenol acid and H2O - a sufficient amount for 100 g of the solution
Distilled at atmospheric pressure to obtain about 70 ml of distillate (74,15 g). This distillate contains 3.2 g of 3-pentenol acid. Vapors have a temperature of 106-107oC and t EXAMPLE 10
In odnogolosy flask 100 ml upload the reaction mixture resulting from the reaction of hydroxycarbonate butadiene in the presence of - -crotyl - palladium-chloride. This mixture has the following composition: 0,0707 g (0,357 mmol) krotil-palladium-chloride, 0,2706 g chlorobutane (or Cotillard), 8.0 g of 3-pentenol acid and 9.1 g of 2-methylglutaric acid and 3,11 2-adelantarnos acid.To this reaction mixture was added 21 g of dichloroethane and 21 g of 20% aqueous hydrochloric acid solution.The flask with a refrigerator placed in an oil bath.Stand the mixture under stirring at 40oC for 1 hAfter stopping stirring and decanting from each of the received two liquid phases take samples for the quantitative determination of palladium.Again find that almost all of the palladium present in the original mixture.The mass ratio distribution of the water layer/organic layer is equal to 32. 1. A way of separating at least part of the palladium from the solution coming after reaction hydroxycarbonylmethyl butadiene in partenavia acid containing at least 3-pontenova acid, characterized in that th is C, of which the aqueous phase contains at least part of palladium.2. The method according to p. 1, characterized in that the aqueous solution of hydrochloric acid containing 5 to 40 wt.% hydrochloric acid based on the weight of the solution.3. The method according to p. 1 or 2, characterized in that an aqueous solution of hydrochloric acid added at the rate of 0.1 to 2-fold volume to the volume of the treated solution.4. The method according to PP.1 to 3, characterized in that the receipt of two liquid phases upon acidification is the result of simply adding an aqueous solution of hydrochloric acid.5. The method according to p. 4, characterized in that the treated solution contains a solvent, generally not miscible with water, such as aromatic, aliphatic or cycloaliphatic hydrocarbons, chlorinated aromatics, chlorinated aliphatic or chlorinated cycloaliphatic hydrocarbon.6. The method according to PP.1 to 3, characterized in that the receipt of two liquid phases occurs as a result of adding an organic solvent not miscible with water, after acidification, at the time of acidification or, if necessary, before acidification.7. The method according to p. 6, characterized in that the organic races of alifaticheskih hydrocarbons, chlorinated aromatics, chlorinated aliphatic or chlorinated cycloaliphatic hydrocarbons, liquid under the operating conditions and generally not miscible with water.8. The method according to p. 6 or 7, characterized in that the organic solvent is chosen among benzene, toluene, xylenes, chlorobenzene, cyclohexane, butadiene, butenes, alkanes, such as hexane, heptane, octane, nonanes, decanes, undecane, dodecane, and various mixtures of several of these solvents.9. The method according to PP.1 to 8, characterized in that the two liquid phases after decanting represent the organic phase, containing more than half of the initial amount pentenoic acids, the major amount of butadiene and butenes, and a part of the dicarboxylic acids may be present in the treated solution, and the aqueous phase, containing more than half the number of palladium, and a part of the dicarboxylic acids may be present in the treated solution.10. The method according to PP.1 to 9, characterized in that the aqueous phase containing palladium, recycle into a new reaction hydroxycarbonylmethyl butadiene preferably after the distillation part of the hydrochloric acid contained in the aqueous phases of the simulation.11. The method according to p. 10, characterized in that the hydrochloric acid obtained by distillation and the corresponding azeotropic mixture of water/hydrogen chloride, is used for acidification original solution, if necessary after adding the additional amount.12. The method according to PP. 1 - 11, characterized in that the treated solution before acidification with an aqueous solution of hydrochloric acid is distilled off at least part pentenoic acids.13. The method according to p. 12, characterized in that the distillation is carried out at a temperature less than or equal to 110oC, more preferably at a temperature of less than or equal to 105oIn order to avoid deposition of palladium.14. The method according to p. 12 or 13, characterized in that the distillation is carried out at atmospheric pressure or a pressure below atmospheric, in the range of 2 to 7 kPa.15. The method according to PP. 12 to 14, characterized in that the residue obtained after the distillation, containing palladium, treated with an aqueous solution of hydrochloric acid.16. The method according to p. 15, characterized in that the aqueous solution of hydrochloric acid containing 5 to 40 wt.% hydrochloric acid based on the weight of the distillation residue.17. The way the share of hydroxycarbonate butadiene, if necessary, after distillation of the excess of hydrochloric acid.
FIELD: processes catalyzed by metal-phosphoro-organic ligand complexes when target product may be selectively extracted and separated from liquid product.
SUBSTANCE: Specification gives description of methods of separation of one or several products of decomposition of phosphoro-organic ligand, one or several reaction byproducts and one or several products from liquid reaction product synthesized continuously and containing one or several non-consumed reagents, catalyst in form of complex of metal-phosphoro-organic ligands, not obligatory free phosphoro-organic ligand, one or several said decomposition products of phosphoro-organic ligand, one or several said reaction byproducts, one or several said products, one or several non-polar solvents and one or several polar solvents by separation of phases where (i) is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several products expressed by ratio of distribution coefficient Ef1 whose magnitudes exceeds about 2.5; (ii)is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several decomposition products expressed by ratio of distribution coefficients Ef2 whose magnitude exceeds proximately 2.5; and (iii) is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several reaction byproducts expressed by ratio of distribution coefficients Ef3 whose magnitude exceeds approximately 2.5 (versions). Description is also given of continuous methods of obtaining one or several products (versions) and reaction mixture containing one or several aldehyde products.
EFFECT: increased conversion of initial materials and selectivity by product; avoidance or exclusion of deactivation of catalyst.
20 cl, 2 tbl
FIELD: industrial organic synthesis catalysts.
SUBSTANCE: invention relates to regeneration of basic anionite catalysts for process of production of alkylene glycols via hydration of corresponding alkylene oxides. Method according to invention consists in treatment of spent catalyst with aqueous solution of inorganic salts of iodine and inorganic acids or with hydroiodic acid aqueous solution.
EFFECT: achieved complete restoration of initial volume and selectivity of catalyst and thereby prolonged lifetime of expensive anionite catalyst.
1 tbl, 8 ex
SUBSTANCE: method involves, for example: (a) evaporation of said oxidised discharge stream, containing terephthalic acid, metallic catalyst, impurities, water and solvent, in the first zone of an evaporator to obtain a vapour stream and a concentrated suspension of the discharge stream; and (b) evaporation of the said concentrated suspension of the discharge stream in the second zone of the evaporator to obtain a stream rich in solvent and a high-concentration suspension of the discharge stream, where the said second zone of the evaporator has an evaporator operating at temperature ranging from 20°C to 70°C, where from 75 to 99 wt % of the said solvent and water is removed by evaporation from the said oxidised discharge stream at step (a) and (b); (c) the said high-concentration suspension of the discharge stream is filtered in a zone for separating solid products and liquid to form a filtered product and a mother liquid; (d) washing the said filtered product using washing substances fed into the said zone for separating solid products and liquid to form a washed filtered product and washing filtrate; and dehydration of the said filtered product in the said zone for separating solid products and liquid to form a dehydrated filtered product; where the said zone for separating solid products and liquid has at least one pressure filtration device, where the said pressure filtration device works at pressure ranging from 1 atmosphere to 50 atmospheres; (e) mixing water and optionally extractive solvent with the said mother liquid and with all of the said washing filtrate or its portion in the mixing zone to form an aqueous mixture; (f) bringing the extractive solvent into contact with the said aqueous mixture in the extraction zone to form a stream of extract and a purified stream, where the said metallic catalyst is extracted from the said purified stream.
EFFECT: improved method of extracting metallic catalyst from an oxidised discharge stream obtained during production of terephthalic acid.
36 cl, 3 dwg, 2 tbl, 2 ex
SUBSTANCE: invention describes method for extraction of homogeneous ruthenium catalyst from glycolic acid hydrogenation reaction product, glycolic acid esters and/or glycolic acid oligomers under action of extractant containing hydrophobic solvent and optional hydrophilic solvent. Ruthenium catalyst, which may include 1,1,1-tris(diaryl- or dialkylfosfinomethyl)alkane ligands, can be extracted from hydrophobic extract phase as result of extraction under action of hydrophilic solvent and sent for recycling in process of producing ethylene glycol as result of glycolic acid and glycolic acid derivatives hydrogenation.
EFFECT: technical result is effective method of ruthenium-1,1,1-tris(diaryl- or dialkylfosfinomethyl)alkane catalyst compositions extracting from glycolic acid hydrogenation waste product till maximum extraction of catalyst system at minimal costs in combined method, taking into account stages of both reaction and separation for producing ethylene glycol.
29 cl, 7 dwg, 26 tbl, 17 ex
SUBSTANCE: present invention relates to methods of producing a hydroformylation catalyst solution for storage, wherein catalyst solution contains: A. a transition metal in combination with one or more organophosphorus ligands, (B). a certain concentration of acid particles and C. water. First version of method includes a step for reducing concentration of acid particles in catalyst solution to not more than 200 ppm. Second version of method includes a step of mixing catalyst solution with aqueous buffer solution, containing one or more materials, which will neutralise and/or absorb, at least 50 % of acid particles.
EFFECT: proposed versions of method enable to reduce degradation of organophosphorus ligands during temporary suspension of hydroformylation process.
SUBSTANCE: method of hydrotreating diesel fuel at a temperature of 340-390°C, pressure 3-9 MPa, volumetric consumption of raw materials 1.0-2.5 h-1, volume ratio hydrogen/raw materials 300-600 m3/m3 in the presence of a regenerated catalyst having a pore volume of 0.3-0.8 ml/g, a specific surface area of 150-280 m2/g, an average pore diameter of 6-15 nm, including molybdenum, cobalt, sulfur and a carrier in its composition is described. Molybdenum and cobalt are contained in the catalyst in the form of a mixture of complex compounds Co(C6H6O7), H4[Mo4(C6H5O7)2O11], H3[Co(OH)6Mo6O18], sulfur is contained in the form of sulfate anion SO42-, in the following concentrations, wt %: Co(C6H6O7) - 5,1-18,0; H4[Mo4(C6H5O7)2O11] - 7,5-15,0; H3[Co(OH)6Mo6O18] - 4,3-19,0; SO42- - 0,5-2,30; carrier - the rest. Cobalt citrates can be coordinated to molybdenum citrate H4[Mo4(C6H5O7)2O11] and to 6-molybdocobaltate H3[Co(OH)6Mo6O18].
EFFECT: invention makes it possible to produce hydrotreated diesel fuels containing not more than 10 ppm of sulfur in the presence of regenerated catalysts.
3 cl, 2 tbl, 6 ex
SUBSTANCE: treatment method involves flowable hydroformylation reaction product contacting with an aqueous buffer solution to neutralise at least some of the acid phosphorus compound to form a neutralised acid phosphorus compound. The hydroformylation reaction product comprises an acidic phosphorus compound, a metal complex catalyst with an organophosphorus ligand that contains a group 8, 9 or 10 metal complex forming an organophosphorus ligand complex and optionally a free organophosphorus ligand. The buffer solution contains at least one unsaturated aliphatic carboxylic acid salt. Salt concentration in the buffer solution is 0.001-0.8 M and the pH value of the buffer solution is in the range of 6-8.
EFFECT: effective buffer removal of acid by-products from phosphite ligand degradation and promotion of selective hydrolysis of diorganophosphite by-products without adverse effect on the hydroformylation process.
7 cl, 1 tbl, 2 ex
SUBSTANCE: invention concerns method of hydrotreating catalyst activation containing metal oxide of group VIB and metal oxide of group VIII containing contacting catalyst, acid and organic additive with boiling point within 80-500°C and water solubility, at least, 5 gram per litre (20°C, atmospheric pressure), optionally with following drying in the environment providing at least, 50% of the additive remains in the catalyst. There are disclosed hydrotreating catalyst produced by the method described above, and method of hydrotreating raw hydrocarbons there after applied.
EFFECT: higher activity of both raw hydrotreating catalyst, and utilized hydrotreating catalyst being regenerated.
20 cl, 8 ex
FIELD: process engineering.
SUBSTANCE: invention relates to production of automotive catalysts, particularly, to their recovery. Method or recovery comprises thermal decomposition of pyrocarbon, dissolution of platinoids by the mix of hydrochloric acid and nitric acid, or 30%- hydrogen peroxide in closed cycle. Note here that dissolution process is analysed for completeness of platinoids extraction while excess nitric acid and hydrogen peroxide are removed by reducing agents. To extract platinoids, acid solution is subjected to ionic flotation extraction by cationic surfactants. Then, extract with platinoid precursors is separated from acid solution containing cerium and aluminium ions to evaporate extractant. Platinoid precursors are dissolved in water to produce micellar solution, added is hydrazine hydrate to reduce platinoids in alkaline medium to metal nanoparticles on mixing by ultrasound. Dispersion is centrifuged to drain aqueous solution and rinse centrate by alcohol to proceed with centrifugation to obtain nanopowder of platinoids. Acid solution containing ions of cerium and aluminium is neutralised by potassium hydroxide to pH=8-9. Potash soap of higher carbonic acids is added to separate cerium and aluminium soaps. The latter are dissolved in micellar aqueous solution of sodium dodecylsulphate to make the mix of cerium and aluminium hydroxides and centrifuge obtained dispersion. Precipitate of cerium and aluminium hydroxides are rinsed by water to be centrifuged again so that precipitate is separated and air dried. Then, said precipitate is calcined at 400°C to obtain nanopowders CeO2 and γ-Al2O3 and CeO2.
EFFECT: new catalysts produced with no extra treatment.
5 cl, 2 ex
SUBSTANCE: invention relates to recovery of hydrocracking catalyst with suspended layer, which includes: separation (120) of exhaust flow (100) from hydrocracking zone (35) with suspended layer on first part (125), including solvent and clarified resin, and second part (130) including resin and catalyst; contacting (140) of second part (130) with acid (145) for leaching of catalyst from resin for producing aqueous solution (170) and residue (165) resin; and contacting (200) aqueous solution (170) with anion (205) to produce insoluble salt (225) and second aqueous solution (220), where insoluble salt (225) is catalyst.
EFFECT: technical result consists in improved method of regenerating hydrocracking catalyst with suspended layer.
10 cl, 2 dwg
SUBSTANCE: method involves thermal decomposition of calcium hypochlorite with stirring with hot steam in the presence of a nichrome catalyst treated in a pickling tank with a solution of hydrochloric acid. In the spent hydrochloric acid solution formed during the processing of the nichrome catalyst after its use in the process of thermal decomposition of calcium hypochlorite, the content of active chlorine is determined. When the spent hydrochloric acid solution is stirred, a solution of sodium thiosulfate is gradually added. The amount of sodium thiosulfate solution in the spent hydrochloric acid solution is maintained at 5-15 times excess from the stoichiometrically necessary one. The neutralized solution is drained into sewage.
EFFECT: reducing toxic substances and active chlorine in wastewater.
5 cl, 1 ex