WO2010119448A1 - Catalyseur amélioré, préparé « in situ » pour synthèse continue de butynediol basse pression - Google Patents

Catalyseur amélioré, préparé « in situ » pour synthèse continue de butynediol basse pression Download PDF

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WO2010119448A1
WO2010119448A1 PCT/IN2009/000271 IN2009000271W WO2010119448A1 WO 2010119448 A1 WO2010119448 A1 WO 2010119448A1 IN 2009000271 W IN2009000271 W IN 2009000271W WO 2010119448 A1 WO2010119448 A1 WO 2010119448A1
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catalyst
reactor
ghsv
hours
prepared
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PCT/IN2009/000271
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Bapurao Sidhram Shinde
Amod Madhukar Sathe
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Hindustan Organic Chemicals Limited
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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/843—Arsenic, antimony or bismuth
    • B01J23/8437—Bismuth
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2286—Alkynes, e.g. acetylides
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
    • B01J31/403—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing iron group metals or copper
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • US Patent #3,560,576 describes a slurry reactor with 6.7% w/v catalyst loading of fine powered malachite based catalyst precursor with 10 to 20 microns particle size at 50 to 120 0 C and pressure below 2 atmospheres for cuprous acetylide catalyst generation and subsequent ethynylation of formaldehyde solution.
  • US Patent #3,954,669 reports preparation of manassite from nitrates of copper, magnesium and aluminium with mixture of sodium carbonate and hydroxide which is then converted to cuprous acetylide complex in slurry reactors.
  • the particle size of the catalyst is less than 100 microns and is used in batch reactor as well as CSTR in loading of 3.8 to 7.4% w/v.
  • the reaction is at nearly atmospheric pressure at 65 to 90 0 C and the catalyst shows high activity.
  • Polish patent #1,35,195 reports a much larger particle size in the range of 0.1 to 0.4 mm under nearly same operating conditions, for a supported catalyst (activated charcoal etc.) with significantly higher (10.8% w/v) catalyst loading in intensively stirred batch slurry reactor. It claims much improved catalyst activity corresponding to its particle size as well as absence of tarry substances (in the product) usually formed at higher temperatures which are difficult to separate from the products. It also eliminates the use of higher temperatures (more than 350 0 C) reported in the earlier work thereby eliminating exposure to nitrogen oxides fumes and related environmental problems.
  • Butynediol synthesis is carried out in this particular case with formaldehyde and propargyl alcohol using 3 to 15% w/v catalyst loading at 90 0 C and nearly atmospheric pressure.
  • the main disadvantages of using the fine powder catalysts in the slurry reactors is their handling and effective separation aspects. Another part associated with them is the catalyst precursor as well as catalyst (cuprous acetylide complex) is prepared separately, and is subsequently charged to the reactor. This involves safe handling part for cuprous acetylide, which is very much critical on the industrial scale.
  • the catalyst activities reported for these catalysts are very much on the higher side, it is mainly attributed to their very fine particle size. Their equivalent activity for a bigger particle size (say 2 to 5 mm) is far from satisfactory for industrial scale operation. Also most of these patents do not report the catalyst life, which is another limitation.
  • the main objective of the invention is to arrive at a 'in-situ' prepared catalyst precursor based on alumina or any other suitable support, eliminating the environmental problems associated with oxides of nitrogen liberated during its preparation. Moreover the precursor is to be used immediately after cuprous acetylide formation, for continuous packed bubble column industrial reactors, operated at pressure just above atmospheric pressure and in temperature range of 50 to 100 0 C.
  • the catalyst should be used effectively for ethynylation of formaldehyde, without the need for dosing of alkali to the reactor to maintain pH.
  • Another objective is that the catalyst size has to be such that solids carry over and further separation from liquid is avoided to result in trouble free, safer operation for long periods.
  • the catalyst shape should also be such that heat dissipation from individual particles to bulk fluid, is fast enough to prevent any localized hot spots, which may cause heavier side products formation, which affect not only butynediol product quality, but that of down stream product too and may cause catalyst agglomeration, thereby high pressure drop through the reactor.
  • the objective is to utilize catalyst is right proportion with suitable inerts to constitute a mixed bed.
  • the objective of the invention is to develop a catalyst which shows good scale-up ability suitable for industrial operation and can be regenerated in an easier manner.
  • the present invention discloses an 'in-situ' prepared catalyst precursor on industrial support, available in suitable shapes and sizes with or without combination with inerts for packed bubble column continuous reactor operation.
  • the precursor is prepared using copper/bismuth nitrates and aqueous alkali in eco-friendly manner and converted to corresponding cuprous acetylide complex for ethynylation of formaldehyde at low pressure and temperature.
  • the catalyst shows high activity, life and can be regenerated in-situ for more cycles, thus reducing considerably the catalyst disposal problems.
  • the industrial support used is alumina spheres in a smaller single tube reactor, the aqueous alkali used being sodium carbonate, the outlet product clear enough, not requiring filtration or any other solid-liquid separation step in further purification processes.
  • the reactor used is a single tube reactor (which can correspond to a single tube of a multi-tubular industrial scale reactor), with a scale-up ratio 17 times that of the smaller single tube reactor, the catalyst being prepared and reactor operated in the same manner as the smaller reactor, showing fair reproducibility in catalyst activity, productivity, and product clarity. Whereas minor variations in catalyst quantity has no effect, steady reaction conditions achieve better activity and productivity for the catalyst. Catalyst lumps/ agglomerates formation is observed especially at the bottom (inlet) of the reactor, which lead to sudden abnormal pressure drop, towards the end of catalyst life.
  • the alkali used is sodium hydroxide, similar conditions for catalyst preparation and ethynylation reaction prevailing, the activity and productivity, as well as deactivation phenomenon of the catalyst are comparable to the lower scale version.
  • use of lower concentration of nitrates leads to lesser activity and productivity.
  • the catalyst can be regenerated in an effective manner using the alkali under inert atmosphere and can be activated by more or less similar procedure to fresh catalyst generation.
  • the catalyst support is mixed with inerts in various proportions, the catalyst prepared and used in a similar manner as before.
  • Such a mixed catalyst bed operation shows high catalyst activity and productivity, due to better heat dissipation from the active particles to inerts in their vicinity and lesser side reactions, thereby.
  • the catalyst support is ring shaped: for better heat dissipation required from the particles for achieving highly steady activity and life (productivity), when prepared and operated under similar manner.
  • the catalyst support in the form of rings of suitable size is mixed with appropriate quantity of inerts and such a mixed catalyst bed prepared and operated in a similar manner for much longer periods, at higher catalyst activity, resulting in a better quality 1,4 butynediol product (without involving filtration / separation step) suitable for better quality downstream products, including 1,4 butenediol, by selective hydrogenation.
  • the industrially available supports preferably alumina for this invention include spheres of 2 to 5 mm diameter, 0.76 to 0.84 g/cc bulk density, 0.3 to 0.5 cc/g pore volume or rings 12 to 16 mm outer diameter x 6 to 9 mm inner diameter x 12 to 16 mm long, with bulk density 0.8 to 1.1 g/cc, pore volume 0.2 to 0.5 cc/g and chemical composition as follows: Oxides of:
  • Aluminium 92% w (min), Sodium: 0.25% w (max), Iron: 0.15 % w (max) and Silicon: 0.15% w (max), with maximum ignition loss of 7%.
  • the catalyst precursor of this invention can be prepared 'in-situ' by the following eco-friendly manner:
  • the inerts may be preferably porcelain rings or saddles, with 3 to 9 mm size with bulk density varying from 0.8 to 1.2 g/cc;
  • Aqueous weak alkali (concentration range from 0 to 5% w) wash for 0 to 24 hours at LHSV 0 to 0.2 h "1 and 20 to 90 0 C temperature, under nitrogen (GHSV 2 to 50 h "1 ), followed by :
  • the aqueous formaldehyde may be ion exchange treated in a concentration range of 15 to 37% w, preferably 10 to 20 % w, containing acidity (expressed as formic acid) less than 0.023 % w, pH of the solution in the range of 5 to 9, with or preferably without the addition of any alkali.
  • acidity expressed as formic acid
  • pH of the solution in the range of 5 to 9, with or preferably without the addition of any alkali.
  • acetylene gas GHSV is 3 to 50 h "1 and the aqueous formaldehyde LHSV is 0.01 to 0.6 h " ', whereas the reaction is carried out at 50 to 100 0 C, preferably 70 to 95 0 C and below 2 atmospheres pressure, preferably just above atmospheric pressure.
  • the continuous single tube reactor smaller as well as bigger versions are made up of stainless steel, with jacketed arrangement for cooling (with cooling water) or alternatively heating (with steam) whenever required to maintain the reactor temperature. It has two separate inlets for liquid and gas at the bottom. Liquid overflow arrangement as well as gas outlet after a gas-liquid separator is provided at the top of the reactor. The gas outlet is passed through a water seal. Liquid is introduced with the help of metering pumps from stainless steel storage tank, whereas gas is provided from gas cylinders, with the help of pressure regulators. All the runs are carried once through. In a multi tubular industrial setup, gas recycle arrangement can be easily done.
  • the reactor is subsequently run continuously for a period of 15 to over 100 days, under the above parameters.
  • the operation is discontinued whenever the reactor pressure drop increases rapidly beyond 0.5 atmospheres or there is significant reduction in catalyst activity.
  • the catalyst can be regenerated effectively in the following manner:
  • alkali wash (preferably sodium hydroxide) for 24 to 48 hours at 20 to 35 0 C, at LHSV 0.01 to 0.6 IT 1 , GHSV 3 to 50 h " ⁇ followed by demineralized water wash under the same conditions, till neutral pH;
  • the regenerated catalyst can be run under the same process conditions with activity of 60 to 100% as that for the fresh catalyst.
  • the catalyst of this invention has been effectively used in a single tube reactor and can be used in similar or multi tubular continuous industrial reactors for long periods of operation at higher activity and better regeneratability and can produce 1,4 butynediol suitable for better quality downstream products, including 1,4 butenediol, produced by selective hydrogenation.
  • Activated alumina spheres size 2 to 5 mm diameter, surface area 300 to 375 m 2 /g pore volume 0.3 to 0.5 cc/g, bulk density of 0.76 to 0.84 (0.8) g/cc, with the chemical analysis, given in Table 1 were packed in a continuous packed bubble column single tube reactor made up of stainless steel, with a cooling water jacketed arrangement for heat removal, as well as heat up arrangement with steam, whenever required.
  • the reactor had separate inlets for gas and liquid at the bottom as well as separate outlets for both at the top.
  • the above solution was slowly introduced from the bottom of the reactor (through the liquid inlet) maintained at 60 0 C, till overflow is observed from the liquid outlet at the top. During this impregnation step, the gas vent was kept open. The period for impregnation was 12 hours. After this, the excess solution was drained from the bottom of the reactor and the quantity measured to know the quantity of solution impregnated on the support.
  • step 4 the impregnated mass was dried under nitrogen introduced from the reactor bottom, in a similar manner as mentioned in step 2. Thereafter the reactor was cooled to ambient temperature (30 0 C ).
  • Alkali in the form of 15% w sodium carbonate solution was prepared and passed through the same reactor via liquid inlet at the reactor bottom, with the help of a metering pump with LHSV of 0.4 h "1 . Nitrogen was introduced from gas inlet at the rector bottom with GHSV 10 h "1 and outlet gases vented off through water seal. Liquid from the reactor outlet at the top was also collected separately. This was continued for 2 to 3 hours at 20 to 30 0 C.
  • the catalyst precursor thus produced 'in-situ' was subsequently converted to cuprous acetylide complex in the reactor itself, as follows:
  • the same reactor was run continuously for 55 days with 20% w formaldehyde feed of the earlier specifications at an average LHSV 0.044 h '1 and GHSV 11.1 h '1 under slightly positive pressure (water seal) at a temperature range of 70 to 80 0 C.
  • the catalyst exhibited an average activity of 130 to 15O g butynediol/kg catalyst per day and a productivity of 7.3 to 10 kg butynediol per kg of catalyst charge was obtained.
  • Example 1 Activated alumina spheres with the properties as described in Example 1 were packed in a continuous packed bubble column made up of stainless steel as before, the rector being a scaled up version 1 :17 times that of the reactor, as described in Example 1. All other reactor arrangements were similar to those mentioned in Example 1.
  • the catalyst precursor thus prepared was subsequently converted to cuprous acetylide complex in the reactor itself as follows: 7. 20% w aqueous formaldehyde with the same specifications as those described in Example 1, was introduced from the reactor inlet under LHSV 0.03 to 0.06 h "1 , with reactor temperature maintained at 70 0 C.
  • the catalyst precursor as well as copper acetylide complex prepared and further reaction carried out in a manner similar to Examples 2 to 5, except that step 5 described therein being eliminated.
  • Runs had to be discontinued when there was a sharp rise in reactor pressure drop from 0.1 to more than 0.6 atmospheres.
  • the product acidity correspondingly, increased from 0.5 to 1.5% w.
  • the discharged catalyst showed agglomerates formation near the reactor inlet portion.
  • the average reactor temperature was maintained at 25 to 50 0 C, subsequently after stopping nitrogen.
  • aqueous formaldehyde (containing formic acid less than 0.023% w by ion exchange resin treatment) with a pH 5 to 6 was introduced from reactor inlet LHSV 0.06 to 0.1 1 h "1 , under nitrogen GHSV 10 to 12 h ⁇ ⁇ for 0 to 4 hours and at temperature 70 to 90 0 C.
  • the reactor temperature was maintained at 70 0 C after stopping nitrogen.
  • Concentrated nitric acid Quantity just adequate to dissolve the above solids.
  • Impregnation of the same in the reactor itself was carried out in a similar manner as described in Example 8. 4.
  • the impregnated mass was dried in a similar manner as described in Example 8.
  • the reactor was run continuously for 26 days with 10% w average formaldehyde of earlier specifications described under average LHSV 0.22 h '1 , average GHSV 1 1.76 h "1 , under slightly positive pressure (as described earlier), in a temperature range of 70 to 80 0 C. Under these conditions, the average catalyst activity obtained was 125 g butynediol/kg catalyst-day and productivity 2.1 kg butynediol/kg-catalyst charge.
  • Activated alumina spheres with the same specifications as described in the earlier Example 8 were taken in the same reactor as described therein.
  • the catalyst precursor, and thereafter copper acetylide complex were also prepared in a similar manner as described therein.
  • the reactor was run continuously in a temperature range of 70 to 80 0 C, under GHSV 11.76 h “1 and LHSV 0.12 to 0.2 h "1 and 15% w formaldehyde conforming to the earlier specifications.
  • the catalyst activity achieved was 240 to 336 g butynediol/kg-cat-day and productivity 1.4 to 2.2 kg butynediol/kg- catalyst.
  • the catalyst regeneration was carried out in the following manner :
  • the reactor was cooled down to 20 to 35 0 C, and then the reactor mass was displaced completely with demineralized water;
  • Acetylene gas was displaced with nitrogen at 20 to 35 0 C for 24 hrs, at the same space velocity of acetylene as before;
  • the mixed bed contained 60% v of the catalyst and balance inerts, described earlier. All other steps involved in part (A) were repeated for catalyst precursor / copper acetylide complex preparation in the same manner as described therein.
  • the reactor was run continuously for a period of 70 to 100 days with 0 to 15% w aqueous formaldehyde solution of earlier specifications and without any alkali added to it, at LHSV 0.15 to GHSV 11.76 h "1 and average reaction temperature 70 to 90 0 C. Under these conditions the catalyst activity and productivity for the mixed bed are shown in Table 3.
  • Reactor temperature was maintained at 90 0 C.
  • Catalyst precursor as well as copper acetylide complex were prepared by the following method :
  • Drying of the support was carried out for a period of 50 to 120 hours at 70 to 90 0 C under nitrogen GHSV 20 IT 1 .
  • step 5 Afterwards nitrogen was stopped as described in step 2 and copper nitrate / bismuth nitrate solution of earlier concentration was again impregnated in the reactor itself in similar manner described in step 3 and drying of impregnated mass was carried out in similar manner as described in step 4.
  • step 5 The sequence as described in step 5 was repeated once more. 7. Thereafter 10% sodium hydroxide solution (alkali) was passed through the reactor LHSV 0.1 to 0.2 h “1 under nitrogen gas GHSV 17 to 27 h "1 for 4 to 5 hours under a temperature of 25 to 40 0 C .
  • alkali sodium hydroxide solution
  • reaction runs were restarted under the same conditions as described before.
  • the regenerated catalyst exhibited 75% activity and runs were carried out for one more month after regeneration.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

L'invention porte sur un catalyseur préparé « in situ » pour l'éthynylation basse pression. Jusqu'à maintenant, les précurseurs de catalyseur d'éthynylation étaient souvent préparés séparément, puis chargés dans des réacteurs appropriés pour la conversion en complexes d'acétylure cuivreux actifs. Dans la présente méthode de préparation de catalyseur, un support de forme et de dimension appropriées est initialement chargé directement dans le réacteur. Le support est ensuite imprégné par des sels métalliques et séché. Des étapes de lavage alcalin suivent, et le catalyseur est ensuite activé par réaction avec de l'acétylène et du formaldéhyde. Le catalyseur résultant fournit une activité élevée, une longue durée de vie et des produits d'éthynylation de bonne qualité. Il est facile d'effectuer une extrapolation sans perte de rendement à l'aide de réacteurs à un ou à plusieurs tubes à échelle industrielle. La consommation de NOx rend la préparation du catalyseur écologique et la facilité de la régénération réduit les problèmes d'élimination.
PCT/IN2009/000271 2009-04-17 2009-05-06 Catalyseur amélioré, préparé « in situ » pour synthèse continue de butynediol basse pression WO2010119448A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014150327A1 (fr) * 2013-03-15 2014-09-25 Basf Corporation Nouveau catalyseur d'éthynylation et procédé de fabrication associé
WO2017035133A1 (fr) * 2015-08-25 2017-03-02 Basf Corporation Catalyseurs à base de butynediol séchés par pulvérisation
CN108069825A (zh) * 2016-11-11 2018-05-25 中国石油化工股份有限公司抚顺石油化工研究院 一种提高甲醛和乙炔反应制备1,4-丁炔二醇催化剂使用周期的方法
CN110540489A (zh) * 2019-09-17 2019-12-06 凯莱英生命科学技术(天津)有限公司 乙炔与酮类化合物进行加成反应的方法
WO2021051275A1 (fr) * 2019-09-17 2021-03-25 凯莱英生命科学技术(天津)有限公司 Procédé pour effectuer une réaction d'addition entre de l'acétylène et un composé cétone

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3920759A (en) * 1972-04-24 1975-11-18 Gaf Corp Ethynylation catalyst and method of producing alkynols by low pressure reactions
US3954669A (en) * 1973-11-20 1976-05-04 Basf Aktiengesellschaft Process for making an ethynylation catalyst
US3957888A (en) * 1974-05-03 1976-05-18 Basf Aktiengesellschaft Process for the manufacture of butynediol
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