WO2015018710A1 - Verfahren zum entfernen von cobaltablagerungen in einem olefin hochdruckhydroformylierung reaktor - Google Patents
Verfahren zum entfernen von cobaltablagerungen in einem olefin hochdruckhydroformylierung reaktor Download PDFInfo
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- WO2015018710A1 WO2015018710A1 PCT/EP2014/066372 EP2014066372W WO2015018710A1 WO 2015018710 A1 WO2015018710 A1 WO 2015018710A1 EP 2014066372 W EP2014066372 W EP 2014066372W WO 2015018710 A1 WO2015018710 A1 WO 2015018710A1
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- Prior art keywords
- nitric acid
- aqueous nitric
- cobalt
- reactor
- treatment
- Prior art date
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 42
- 239000010941 cobalt Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 41
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 26
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 113
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 113
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 44
- 239000007789 gas Substances 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 22
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 19
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 230000008859 change Effects 0.000 claims description 10
- 150000001868 cobalt Chemical class 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 9
- 229910001882 dioxygen Inorganic materials 0.000 claims description 9
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 230000002123 temporal effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000005201 scrubbing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- VWGMCGRTCLVGQL-UHFFFAOYSA-L cobalt(2+) dihydroxide hydrate Chemical compound [OH-].O.[Co+2].[OH-] VWGMCGRTCLVGQL-UHFFFAOYSA-L 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DFVOXRAAHOJJBN-UHFFFAOYSA-N 6-methylhept-1-ene Chemical compound CC(C)CCCC=C DFVOXRAAHOJJBN-UHFFFAOYSA-N 0.000 description 1
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000003926 complexometric titration Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0438—Nitric acids or salts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/002—Avoiding undesirable reactions or side-effects, e.g. avoiding explosions, or improving the yield by suppressing side-reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2455—Stationary reactors without moving elements inside provoking a loop type movement of the reactants
- B01J19/246—Stationary reactors without moving elements inside provoking a loop type movement of the reactants internally, i.e. the mixture circulating inside the vessel such that the upward stream is separated physically from the downward stream(s)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto
- B08B9/08—Cleaning containers, e.g. tanks
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00245—Avoiding undesirable reactions or side-effects
- B01J2219/00247—Fouling of the reactor or the process equipment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00245—Avoiding undesirable reactions or side-effects
- B01J2219/00252—Formation of deposits other than coke
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/20—Industrial or commercial equipment, e.g. reactors, tubes or engines
Definitions
- Cobalt-catalyzed high pressure hydroformylation is an important step in the production of higher branched alcohols from higher branched olefins, such as the production of isononanol from isooctene.
- the aldehyde has an additional carbon atom compared to the olefin.
- the reaction is generally carried out in a reactor at temperatures of 120 to 240 ° C under a synthesis gas pressure of 150 to 400 bar.
- multistage processes For cobalt-catalyzed high-pressure hydroformylation, multistage processes have been developed which make it possible to separate the catalyst leaving the reactor with the hydroformylation products from the hydroformylation products and to recycle it into the hydroformylation reaction.
- Such a process may include the 4 process stages of precarbonylation, catalyst extraction, olefin hydroformylation and decobalting.
- the z. B Cobaltformiat or cobalt acetate, by reaction with carbon monoxide and hydrogen of the required for the hydroformylation catalyst HCo (CO) 4 prepared.
- the catalyst prepared in the first process stage is extracted from the aqueous phase with an organic phase, preferably with the olefin to be hydroformylated.
- the organic phase loaded with the catalyst is fed to the olefin hydroformylation.
- the organic phase of the reactor effluent is freed from the cobalt carbonyl complexes in the presence of process water, which may contain formic acid or acetic acid, by treatment with oxygen or air.
- process water which may contain formic acid or acetic acid
- the catalyst is oxidatively destroyed and the resulting cobalt salts are back-extracted into the aqueous phase.
- the aqueous cobalt salt solution obtained from the decobalting is recycled to the first process stage, the precarbonylation.
- the precarbonylation, the catalyst extraction and the olefin hydroformylation can also be carried out in a one-step process in the hydroformylation reactor.
- HCo (CO) 4 is stable only at high partial pressure of CO at the high temperature prevailing in the hydroformylation reactor (see New Synthesis with Carbon Monoxide, J. Falbe, Springer Verlag 1980, page 17, FIG. 1).
- the temperature can be increased and / or the partial pressure of the CO can be reduced so that HCo (CO) 4 decomposes therein.
- metallic cobalt precipitates, causing cobalt deposits.
- the cobalt deposits can cause the reactor is mixed worse.
- the poorer mixing in turn favors the further formation of cobalt deposits.
- the decreasing mixing of the reactor leads to a reduction in the yield of hydroformylation product.
- transition metal deposits which form on the inner walls of a hydroformylation reactor, by cleaning with corrosive liquids such. As aqueous nitric acid, can be removed.
- Aqueous nitric acid can be introduced into the reactor without opening the reactor lid. You can through openings such. B. pipe socket, are introduced into the reactor. Upon dissolution of cobalt deposits by aqueous nitric acid, a nitrogen oxide-containing exhaust gas is formed.
- This object is achieved by a process for removing cobalt deposits in a reactor for cobalt-catalyzed high-pressure hydroformylation of olefins by treatment with aqueous nitric acid, wherein the reactor is at least partially filled with aqueous nitric acid and the temperature of the aqueous nitric acid is increased during the treatment.
- the cobalt deposits are dissolved, whereby the elemental cobalt is oxidized to cobalt (II) compounds which are readily soluble in aqueous nitric acid.
- Nitric acid is reduced with the release of a nitrogen oxide-containing exhaust gas.
- the temperature of the aqueous nitric acid is increased in the course of the treatment when the change over time of the acid concentration and / or the cobalt ion concentration indicates a decrease in the reaction rate.
- the temperature of the aqueous nitric acid is raised from a first temperature in the range of 10 to 40 ° C to a final temperature in the range of 60 to 80 ° C, preferably 70 to 80 ° C, particularly preferably 75 to 80 ° C.
- the temperature of the aqueous nitric acid during the treatment is preferably not increased above 80 ° C.
- the aqueous nitric acid is introduced into the reactor at a first temperature, preferably ambient temperature. First, the treatment is preferably carried out without active supply of heat.
- the temperature is then increased gradually or continuously to a final temperature in the range of 60 to 80 ° C.
- the temperature is preferably increased stepwise by 6 to 40 ° C., preferably 8 to 30 ° C., particularly preferably 10 to 25 ° C., until the final temperature is reached.
- the temperature increase takes place by active supply of heat.
- Suitable, pressure-resistant reaction apparatuses for high-pressure hydroformylation are known to the person skilled in the art. These include the commonly used reactors for gas-liquid reactions, such as. B. tubular reactors, stirred tank, gas circulation reactors, bubble columns, etc., which may optionally be divided by internals again. Suitable, for example, a vertical high-pressure bubble column reactor, which is optionally provided with coaxial tubular internals.
- the reactor used is typically a high-pressure pipe (see, for example, DE 19 38 102) with flanged de disgusting having at least two openings. The openings are preferably in the form of pipe sockets and are used to introduce the reactants and the catalyst and for the discharge of the products.
- the reactor wall is made of pressure-resistant steel and has a stainless steel lining (V2A or V4A).
- the reactor lid does not need to be opened, since the aqueous nitric acid can be introduced into the reactor through other openings when the reactor lid is closed.
- the openings are preferably openings for introducing the educts and the catalyst and for discharging the products. Preferably, these openings are easy-open pipe sockets. This offers over the mechanical removal of cobalt deposits, such. B. by a high-pressure water jet, the advantage that the associated with the opening of the reactor cover and the subsequent pressure-tight re-closing high technical complexity is eliminated.
- a nitrogen oxide-containing offgas which is formed when the cobalt deposits are dissolved in the aqueous nitric acid, is combined with a molecular oxygen-containing gas and at least partially absorbs the offgas in an aqueous liquid.
- the aqueous liquid is z.
- water itself or an aqueous alkaline solution preferably an aqueous sodium hydroxide solution.
- the absorption of the exhaust gas is preferably carried out at a temperature of 10 to 50 ° C.
- the exhaust gas is passed to the aqueous liquid in a scrubbing column and a gas containing molecular oxygen is introduced into the waste gas and / or into the scrubbing column.
- the scrubbing column is preferably a packed column.
- the column contains a packed bed, wherein the exhaust gas is introduced below the bed and gives up the aqueous liquid above the bed.
- the bed of stainless steel preferably comprises existing Pall rings. The packed bed intensifies the contact between the exhaust gas, the aqueous liquid and optionally the molecular oxygen-containing gas.
- the nitrogen oxide-containing exhaust gas contains a high proportion of NO, which is less soluble in water than NO2.
- the resulting degree of oxidation is preferably less than at least 50%, z. B. 50 to 60%.
- the degree of oxidation is defined as the volume fraction of NO2 in relation to the total volume NO + NO2.
- the molecular oxygen-containing gas is preferably used air.
- the molecular oxygen-containing gas is preferably also introduced below the bed or admixed before the column the nitrogen oxide-containing exhaust gas.
- the admixing is preferably carried out under such conditions that a sufficient residence time for the adjustment of the desired degree of oxidation results (data on the reaction kinetics: M. Bodenstein: The rate of reaction between see nitric oxide and oxygen, Z. f., Elektroch., 24, p. 1918).
- This can be achieved, for example, by admixing the molecular oxygen-containing gas into a tube or a container through which the nitrogen oxide-containing exhaust gas flows at a low flow rate.
- the wastewater produced in the treatment of the waste gas with water is preferably added to a wastewater treatment.
- the reactor is at least partially filled with aqueous nitric acid.
- the aqueous nitric acid is circulated during the treatment in the reactor. By circulating a mixing of the nitric acid is achieved and increases the dissolution rate of the deposits by avoiding concentration gradients.
- the aqueous nitric acid in the reactor is circulated so fast that it is exchanged once on average at least every three hours, preferably every two hours, preferably every hour (ie with 10 m 3 aqueous nitric acid is preferably recirculated at 10 m 3 / h ).
- the aqueous nitric acid is preferably heated during the circulation while heating a stream of aqueous nitric acid conducted outside the reactor.
- the heat is preferably supplied via a heat exchanger or an electric heater.
- an internal cooling system of the reactor to heat the aqueous nitric acid.
- the internal cooling system is used during production to dissipate the heat of reaction. It is usually designed so that the reactor contents can also be heated with the internal cooling system.
- a stream of nitric acid is withdrawn at the bottom of the reactor and reintroduced at the top of the reactor. It is preferable to use a pump to give up the withdrawn nitric acid.
- the replenishment is preferably such that cobalt deposits that are Be located above the liquid level of nitric acid in the reactor, are wetted as completely as possible with the aqueous nitric acid.
- the aqueous nitric acid is passed before entering the pump through a filter which prevents the entry of solids such. B. detached particulate deposits prevented in the pump.
- the reactor is filled with the aqueous nitric acid to a maximum of 70%, preferably to a maximum of 60%, particularly preferably to a maximum of 50%.
- the reactor is filled with at least 1%, preferably at least 5%, particularly preferably at least 10%, with the aqueous nitric acid.
- the reactor is completely filled with aqueous nitric acid, using an overflow vessel for collecting overflowing nitric acid.
- an overflow vessel for collecting overflowing nitric acid.
- the acid is discharged from the overflow container and returned to the reactor.
- the nitric acid is preferably recycled by introducing it at the lower end of the reactor. It is preferable to use a pump to recycle the nitric acid.
- the aqueous nitric acid is passed through a filter prior to entering the pump to prevent the entry of solids into the pump.
- the concentration of the initially used aqueous nitric acid is preferably in the range of 100 to 200 g HN0 3 1 "1 .
- a completely or partially exhausted aqueous nitric acid is formed.
- the acid content of the exhausted aqueous nitric acid is insufficient to dissolve further cobalt deposits at a significant reaction rate.
- the aqueous nitric acid is usually exhausted when the concentration of nitric acid falls below 25 g of HNO3 1 "1.
- the acidity of a partially depleted aqueous nitric acid is sufficient to dissolve further deposits of cobalt with appreciable reaction rate partially exhausted when the concentration of nitric acid is below the initially used nitric acid and above 25 g H NO3 1 "1 .
- a partially depleted aqueous nitric acid may be stored for reuse at a later time as aqueous nitric acid in a process of the present invention.
- the acid concentration and / or cobalt ion concentration of the aqueous nitric acid are measured in the course of the treatment.
- the acid concentration is preferably measured by acid-base titration or by means of a pH probe.
- the cobalt ion concentration is preferably measured by complexometric titration.
- the change with time of the acid concentration and / or the cobalt ion concentration results from the measurements which are carried out at different times in the course of the treatment. The measurements are preferably carried out at intervals of 10-300 minutes, preferably 20-180 minutes, particularly preferably 30-120 minutes.
- the temperature of the aqueous nitric acid is preferably increased if the change with time of the acid concentration and / or the cobalt ion concentration falls below a predetermined limit.
- the temperature is preferably increased stepwise by 6 to 40 ° C., preferably 8 to 30 ° C., particularly preferably 10 to 25 ° C., until the final temperature is reached.
- the temperature increase takes place by active supply of heat.
- the temperature of the aqueous nitric acid is raised from a first temperature in the range of 10 to 40 ° C to a final temperature in the range of 60 to 80 ° C, preferably 70 to 80 ° C, particularly preferably 75 to 80 ° C.
- the nitric acid is exhausted.
- the exhausted aqueous nitric acid is let out of the reactor.
- the depleted aqueous nitric acid is then preferably left out of the reactor as soon as the nitric acid concentration drops below 25 g of HNO 3 1 "1 and / or the cobalt ion concentration rises above 85 g If the cobalt deposits are not yet completely removed when exhausted aqueous nitric acid is drained from the reactor, the reactor is preferably filled with fresh aqueous nitric acid and the process repeated.
- the aqueous nitric acid is preferably used in stoichiometric excess, based on the cobalt deposits to be dissolved.
- the amount of cobalt deposited can be estimated from process parameters such as the duration and temperature of the previous productive operation or from the amount of cobalt added during the course of the previous productive operation.
- the treatment according to the invention is carried out in several steps, for. B. by first a partially exhausted aqueous nitric acid is used, which - as soon as it is exhausted - drained and replaced by fresh aqueous nitric acid, enter into the calculation of the available nitric acid amount, the contributions of the individual steps.
- the cobalt-catalyzed hydroformylation reaction is interrupted to prepare the reactor for the treatment with aqueous nitric acid according to the invention.
- this relaxes the reactor and leaves the reaction mixture in the reactor.
- the organic compounds such.
- the organic compounds such.
- the organic compounds such.
- the organic compounds such.
- the organic compounds such.
- the organic compounds such.
- the organic compounds such.
- the organic compounds such.
- the organic compounds such.
- the organic compounds such.
- the organic compounds such.
- the organic compounds such.
- the reactor is cleaned with a jet of water to complete the removal of the cobalt deposits.
- a jet of water preferably a high pressure water jet
- the process is also carried out in this embodiment, without opening the reactor, whereby the with the opening of the reactor lid and associated with the subsequent pressure-tight resealing high technical effort is eliminated.
- a high-pressure water jet is a jet of water produced by applying a pressure of 2 to 500 bar (absolute).
- the residues that remain in the reactor after draining the aqueous nitric acid can be almost completely removed by water or steam.
- the reactor is rinsed with water or steam after the treatment with aqueous nitric acid. Remaining water residues in the reactor do not affect the subsequent hydroformylation process. As a result, only a small effort is required between the cleaning operation (removal of cobalt deposits) and the productive operation (hydroformylation process).
- the oxidation of the cobalt deposits does not come to a halt even if the acid concentration of the aqueous nitric acid has already been reduced and the concentration of cobalt ions in the aqueous nitric acid has risen. Consequently, optionally after repeated use of a partially exhausted aqueous nitric acid, an exhausted aqueous nitric acid having a high cobalt ion concentration of up to 85 gl -1 precipitates in the process according to the invention. From this cobalt can be recovered with little effort. Accordingly, one embodiment of the process in which cobalt is recovered from the spent aqueous nitric acid is particularly preferred.
- a cobalt salt containing hydroxide and / or oxide anions separates from the cobalt salt and the cobalt salt is reacted with acetic acid to a cobalt acetate solution.
- the exhausted aqueous nitric acid is first filtered to separate off the solid which is present, and the filtrate is neutral or slightly basic with sodium hydroxide solution, with cobalt precipitating as cobalt hydroxide hydrate.
- the precipitated cobalt hydroxide hydrate is filtered off and dried on a filter press. The filter cake is reacted by adding acetic acid back to a cobalt acetate solution. It is advantageous if the Cobaltionenkonzentration in the resulting exhausted aqueous nitric acid is as high as possible.
- the recovered cobalt acetate is preferably reused in a hydroformylation process.
- example 1 The recovered cobalt acetate is preferably reused in a hydroformylation process.
- a hydroformylation reactor with an internal diameter of 1.5 m and an internal height of 18 m was emptied thoroughly and then filled several times with hot water and emptied again to remove residues of organic material to a large extent.
- the reactor was charged with 10 m 3 aqueous nitric acid (65 g HNO 3 / l) containing 64 g / l cobalt and having a temperature of 20 ° C. Subsequently, the acid at the bottom of the reactor was withdrawn by means of a pump and added back to the reactor. In this way, about 8 m 3 / h were pumped.
- the resulting exhaust gases together with 20 Nm 3 / h of air, passed from below into a column having an inner diameter of 350 mm, an inner height of 5000 mm and a bed of 25 mm Pallringen with a height of 2500 mm.
- the column was charged from above with 5 m 3 / h of water.
- the wastewater was fed to the wastewater treatment plant.
- the aqueous nitric acid was first heated to a temperature of 35 ° C in the reactor. Within 10 hours, the concentration of aqueous nitric acid dropped to 26 g / L and the cobalt ion concentration increased to 72 g / L. After the cobalt ion concentration did not change for two hours, the solution was drained.
- the reactor was purged with deionized water until the effluent water was neutral.
- a hydroformylation reactor with an internal diameter of 1 m and an internal height of 18 m was emptied thoroughly and then filled several times with hot water and emptied again to remove residues of organic material largely.
- the reactor was charged with 20 m 3 aqueous nitric acid (161 g HNO 3 / l) containing 29 g / l cobalt and having a temperature of 20 ° C with some of the acid overflowing to the postreactor. Subsequently, the acid was withdrawn at the bottom of the secondary reactor by means of a pump and returned to the lower part of the reactor. In this way, about 8 m 3 / h were pumped.
- the resulting exhaust gases were, together with 20 Nm 3 / h of air, passed from below into a column having an inner diameter of 350 mm, an inner height of 5000 mm and a bed with 25 mm Pallringen with a height of 2500 mm had.
- the column was charged from above with 5 m 3 / h of water.
- the wastewater was fed to the wastewater treatment plant.
- the aqueous nitric acid was first heated in the reactor to a temperature of 50 ° C. Within 24 hours, the acid concentration decreased to 120 g / L and the cobalt ion concentration increased to 40 g / L. After another 18 hours, the acid concentration dropped to 107 g / L and then did not change within three hours. After raising the temperature to 70 ° C, the acid concentration dropped to 93 g / l within 12 hours and the concentration of cobalt ion increased to 45 g / l.
- the reactor was purged with condensate until the effluent condensate was neutral.
- a hydroformylation reactor with an internal diameter of 1.5 m and an internal height of 18 m was cleaned by using 10 m 3 of 20% nitric acid.
- the internal circulation time in the reactor was measured by a radioactive shock marking.
- the sodium isotope 24 Na was used as an indicator. The measurements were carried out in two operating conditions, once before the cobalt deposits were removed and once after the cleaning. The speed of the indicator flowing upward in the plug tube was determined to be 25 cm / s before cleaning, and 41 cm / s after cleaning.
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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JP2016532322A JP6657086B2 (ja) | 2013-08-08 | 2014-07-30 | オレフィンの高圧ヒドロホルミル化のための反応器中のコバルト付着物を除去する方法 |
US14/909,852 US10385422B2 (en) | 2013-08-08 | 2014-07-30 | Method for removing cobalt deposits in a high-pressure olefin hydroformylation reactor |
KR1020167005724A KR20160041959A (ko) | 2013-08-08 | 2014-07-30 | 고압 올레핀 히드로포르밀화 반응기에서 코발트 침착물을 제거하는 방법 |
EP14744585.2A EP3030542B1 (de) | 2013-08-08 | 2014-07-30 | Verfahren zum entfernen von cobaltablagerungen in einem olefin hochdruckhydroformylierung reaktor |
CN201480055335.1A CN105636927B (zh) | 2013-08-08 | 2014-07-30 | 除去高压烯烃加氢甲酰化反应器中钴沉积物的方法 |
MYPI2016000194A MY183447A (en) | 2013-08-08 | 2014-07-30 | Method for removing cobalt deposits in a high-pressure olefin hydroformylation reactor |
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EP13179688.0 | 2013-08-08 | ||
EP13179688 | 2013-08-08 |
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WO2015018710A1 true WO2015018710A1 (de) | 2015-02-12 |
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PCT/EP2014/066372 WO2015018710A1 (de) | 2013-08-08 | 2014-07-30 | Verfahren zum entfernen von cobaltablagerungen in einem olefin hochdruckhydroformylierung reaktor |
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US (1) | US10385422B2 (de) |
EP (1) | EP3030542B1 (de) |
JP (1) | JP6657086B2 (de) |
KR (1) | KR20160041959A (de) |
CN (1) | CN105636927B (de) |
MY (1) | MY183447A (de) |
WO (1) | WO2015018710A1 (de) |
Cited By (1)
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US10315182B2 (en) | 2015-12-22 | 2019-06-11 | Basf Se | Cylindrical reactor and use thereof for continuous hydroformylation |
Citations (4)
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DE750498C (de) * | 1942-06-04 | 1953-05-11 | Ig Farbenindustrie Ag | Verfahren zur Entfernung von Eisenverbindungen aus Gemischen von Kohlenwasserstoffenund sauerstoffhaltigen Stoffen |
FR1089983A (fr) * | 1953-06-20 | 1955-03-25 | Ets Kuhlmann | Procédé de récupération du cobalt contenu dans les produits de la synthèse oxo |
EP0024761A1 (de) * | 1979-08-29 | 1981-03-11 | Shell Internationale Researchmaatschappij B.V. | Verfahren zur Herstellung von Alkoholen oder Aldehyden, nach diesem Verfahren hergestellte Alkohole und Aldehyde und zur Verwendung im genannten Verfahren geeignete stabilisierte Zusammensetzungen |
US7910782B2 (en) * | 2007-04-10 | 2011-03-22 | Exxonmobil Chemical Patents Inc. | Cobalt recovery from cobalt catalysed hydroformylation reactions |
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FR2053177B1 (de) | 1969-07-26 | 1973-03-16 | Basf Ag | |
JPS5031858B1 (de) | 1970-12-25 | 1975-10-15 | ||
JPS5438297A (en) * | 1977-09-01 | 1979-03-22 | Nippon Mining Co Ltd | Production of cobalt oxide |
US4139461A (en) | 1977-12-27 | 1979-02-13 | Sterling Drug Inc. | Removal of solids from a wet oxidation reactor |
JPS5585534A (en) | 1978-12-25 | 1980-06-27 | Kuraray Co Ltd | Carbonylation of olefinic compound |
JPS5658545A (en) | 1979-10-19 | 1981-05-21 | Mitsubishi Petrochem Co Ltd | Separating method of oxo reaction catalyst |
GB8907577D0 (en) * | 1989-04-04 | 1989-05-17 | Exxon Chemical Patents Inc | Catalyst recovery in the production of alcohols |
JP2985647B2 (ja) * | 1993-02-26 | 1999-12-06 | 住友金属鉱山株式会社 | 使用済み触媒の溶解方法 |
JP4392537B2 (ja) | 2005-01-17 | 2010-01-06 | 新第一塩ビ株式会社 | スケール付着防止剤の塗布方法 |
US7329783B2 (en) | 2005-06-30 | 2008-02-12 | Shell Oil Company | Hydroformylation process |
JP2012246519A (ja) | 2011-05-26 | 2012-12-13 | Nippon Telegr & Teleph Corp <Ntt> | 金属の浸出方法 |
-
2014
- 2014-07-30 JP JP2016532322A patent/JP6657086B2/ja active Active
- 2014-07-30 CN CN201480055335.1A patent/CN105636927B/zh active Active
- 2014-07-30 WO PCT/EP2014/066372 patent/WO2015018710A1/de active Application Filing
- 2014-07-30 KR KR1020167005724A patent/KR20160041959A/ko not_active Application Discontinuation
- 2014-07-30 EP EP14744585.2A patent/EP3030542B1/de active Active
- 2014-07-30 US US14/909,852 patent/US10385422B2/en active Active
- 2014-07-30 MY MYPI2016000194A patent/MY183447A/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE750498C (de) * | 1942-06-04 | 1953-05-11 | Ig Farbenindustrie Ag | Verfahren zur Entfernung von Eisenverbindungen aus Gemischen von Kohlenwasserstoffenund sauerstoffhaltigen Stoffen |
FR1089983A (fr) * | 1953-06-20 | 1955-03-25 | Ets Kuhlmann | Procédé de récupération du cobalt contenu dans les produits de la synthèse oxo |
EP0024761A1 (de) * | 1979-08-29 | 1981-03-11 | Shell Internationale Researchmaatschappij B.V. | Verfahren zur Herstellung von Alkoholen oder Aldehyden, nach diesem Verfahren hergestellte Alkohole und Aldehyde und zur Verwendung im genannten Verfahren geeignete stabilisierte Zusammensetzungen |
US7910782B2 (en) * | 2007-04-10 | 2011-03-22 | Exxonmobil Chemical Patents Inc. | Cobalt recovery from cobalt catalysed hydroformylation reactions |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US10315182B2 (en) | 2015-12-22 | 2019-06-11 | Basf Se | Cylindrical reactor and use thereof for continuous hydroformylation |
Also Published As
Publication number | Publication date |
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KR20160041959A (ko) | 2016-04-18 |
CN105636927A (zh) | 2016-06-01 |
JP2016529247A (ja) | 2016-09-23 |
JP6657086B2 (ja) | 2020-03-04 |
EP3030542B1 (de) | 2017-06-21 |
CN105636927B (zh) | 2018-10-09 |
MY183447A (en) | 2021-02-18 |
US20160265084A1 (en) | 2016-09-15 |
EP3030542A1 (de) | 2016-06-15 |
US10385422B2 (en) | 2019-08-20 |
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