CN103012103A - Method for preparing acetic acid through catalytic carbonylation reaction - Google Patents

Method for preparing acetic acid through catalytic carbonylation reaction Download PDF

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CN103012103A
CN103012103A CN2012105580837A CN201210558083A CN103012103A CN 103012103 A CN103012103 A CN 103012103A CN 2012105580837 A CN2012105580837 A CN 2012105580837A CN 201210558083 A CN201210558083 A CN 201210558083A CN 103012103 A CN103012103 A CN 103012103A
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reaction
rhodium
acetic acid
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water
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CN103012103B (en
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高山林
赖春波
王苏
李媛
廖本仁
张春雷
揭元萍
曾义红
曹智龙
刘艳
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Shanghai Huayi Group Corp
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Abstract

The invention relates to a method for preparing acetic acid through a catalytic carbonylation reaction, and mainly solves the problems of low stability of rhodium catalyst under the low water condition, low reaction activity when producing the acetic acid through low-water carbonylation, and short product oxidization time. Methanol or derivative of the methanol is adopted as a raw material, and is carbonylated with a liquid reaction composition to synthesize acetic acid; the reaction composition comprises the rhodium catalyst, a halogen promoter, methyl acetate, the acetic acid, water, a iodide-salt cocatalyst and a ruthenium complex used as a stabilizing agent, wherein the ruthenium complex is selected from at least one of [Ru(Co)aIb]n, Mn<+>[Ru(CO)aIb]<->n or Mn<+>[RuIb]<->n. The technical scheme solves the problems better, and can be applied in the industrial production of preparing the acetic acid through the catalytic carbonylation reaction.

Description

The method for preparing acetic acid by the catalyzed carbonylation reaction
Technical field
The present invention relates to a kind ofly prepare the method for acetic acid by catalyzed carbonylation reaction, particularly a kind of ruthenium complex is as the production method of the low water carbonylation acetic acid of catalyst stabilizer.
Background technology
Acetic acid is a kind of eco-friendly organic acid, important chemical intermediate and chemical reaction solvent, can derive hundreds of kind derived product by it, such as Vinyl Acetate Monomer, acetate fiber, aceticanhydride, acetic ester, Mono Chloro Acetic Acid, terephthalic acid, polyvinyl alcohol and metal acetate salt etc., be widely used in the synthetic of medicine, synthon, light industry, weaving, leather, agricultural chemicals, explosive, rubber and metal processing, food and Fine Organic Chemical product.
Producing continuously acetic acid by methyl alcohol or ritalin and carbon monoxide carbonylation reaction, is the method for topmost production acetic acid in the prior art.Patent EP0055618A1 has reported that the rhodium catalyst system can promote reaction under the effect of organic iodine such as methyl-iodide, the water-content of reaction system need to be controlled at 14wt%-15wt%, with the speed of keeping reaction and the stability of rhodium catalyst, thereby so that the operation energy consumption of product greatly increase, and side reaction is more, and this is called as the high-moisture carbonylating process.
Production of Acetic Acid by Methanol Carbonylation technique is strided forward to the low water content scheme by high-moisture.Reactive system composition comprises water amount participates in carbonylation with 14wt% or lower water concentration and produces process of acetic acid.The low water content carbonylating process has reduced water-gas reaction, has reduced water-content and the propionic acid content of acetate products recovery system, thereby alleviated its operational load, finally reduce production cost, embodied the high-efficiency low energy consumption production advantage of low water content carbonylating process.Keep stability and the activity of catalyzer also more difficult when but water concentration further reduces, specifically in the circulating cooling system of reactor and flasher or follow-up pipeline, the catalyst precipitation thing can occur, thereby increase the consumption of catalyzer.Patent US5001259A discloses a kind of by using soluble alkaline earth or basic metal, further promote the method for oxonation and rugged catalyst, but increased the concentration of unsaturated compound such as acetaldehyde, cause easily the potassium permanganate time of product defective, and the impurity concentration of byproduct propionic acid is higher, causes propionic acid tower separating energy consumption high.When the patent EP 0728727B1 of Poole etc. discloses low aquatic product acetic acid by interpolation ruthenium or the combination of osmium metal promoter, but system is carried out not adding lithium iodide or be lower than under the 3wt% condition in lithium iodide concentration, but the stability of the rhodium of this catalysts needs further to improve, after pointing out to add the ruthenium trichloride auxiliary agent among this article embodiment, the deposition rate of rhodium is reduced to 55.6% from 90.7%, and the deposition rate of rhodium is still very high.
Patent CN101146754A has mentioned and has comprised a kind of metal-salt as the acetic acid of catalyst stabilizer, this catalyst system is selected ruthenium salt, at least a metal-salt in pink salt and composition thereof, but the not clear and definite concrete molecular structure that plays the ruthenium metal salt compound of stabilization.Such as the catalyzed reaction liquid that contains carbonyl iodate rhodium to preparation, or to the reaction solution that takes out the acetic acid production device, or to the liquid that takes out flash drum, add acetic acid ruthenium or RuI 3, when in solution with acetic acid ruthenium or RuI 3When existing, rhodium is not played obvious stabilization.Do not provide in addition the example that can below reactive system composition comprises water amount 2wt%, operate in this patent, be unfavorable for further reducing energy consumption.Patent CN1135211C has mentioned a kind of method for preparing Glacial acetic acid, but the diacetyl oxide that comprises 0.1wt%-8wt% in this reactor catalyst composition, thereby in the process of preparation acetic acid, having increased the diacetyl oxide sepn process, diacetyl oxide need to loop back reactive system.Therefore on industrial application, impel the stability that under low water condition, further improves rhodium catalyst by reaction compositional refinements and production technology optimization, keep higher rhodium catalyst concentration, improve carbonylation rate, reduce unit consumption of product, improving the quality of products is the technical problem that present many investigators need to be resolved hurrily.
Summary of the invention
Technical problem to be solved by this invention is the poor stability that there is rhodium catalyst under low water condition in prior art, reactive behavior is low when low water carbonylation is produced acetic acid, the problem that the product potassium permanganate oxidation time is short provides a kind of new catalyzed carbonylation that passes through to react the method for preparing acetic acid.The method has in the stability that can keep rhodium catalyst under the low water condition and still keep its reactive behavior when low water carbonylation is produced acetic acid, and the potassium permanganate oxidation time of improving product, thereby reaches low cost production acetic acid, the advantage of improving the quality of products.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method for preparing acetic acid by the catalyzed carbonylation reaction, described method is included under the existence of carbon monoxide and the rhodium-based catalyst systems that comprises following material, the compound that is selected from alkyl alcohol and its reactive derivatives is reacted in response composite, described alkyl alcohol is methyl alcohol, and rhodium-based catalyst systems comprises following material:
(i) rhodium;
(ii) halogen catalyst;
(iii) iodide salt co-promoter, its concentration so that the iodide ion concentration that produces greater than the 3wt% of response composite; With
(iv) be selected from the stablizer of ruthenium complex, ruthenium complex is selected from [Ru (CO) aI b] n, M N+[Ru (CO) aI b] - nOr M N+[RuI b] - nIn at least a, wherein M is a kind of among H, Li, Na, K, Fe, Ni, Mo, Mn, Cr or the In, a is selected from the positive integer among the 1-4, b is selected from the positive integer among the 1-4, n is selected from the positive integer among the 1-4, described response composite comprises: rhodium catalyst, halogen catalyst, ritalin, acetic acid, water, iodide salt co-promoter, and as the ruthenium complex of stablizer;
Wherein said response composite comprises 0.1wt%-14wt% water, and the mol ratio of ruthenium complex and rhodium is 0.1:1-20:1;
Wherein rhodium-based catalyst systems is illustrated at least catalyst system of 300ppm rhodium metal concentration is provided in the methanol carbonylation composition.
In the technique scheme, the consumption preferable range of rhodium is present in the described response composite for the concentration with the 300ppm-3000ppm of described response composite; The halogen catalyst preferred version is methyl-iodide; The consumption preferable range of halogen catalyst exists for the concentration with the 2wt%-20wt% of described response composite; The iodide salt co-promoter preferred version is lithium iodide; The consumption preferable range of iodide salt co-promoter is that the iodide ion concentration that produces is the concentration existence of the 4wt%-20wt% of response composite; The mol ratio preferable range of ruthenium complex and rhodium is 0.5:1-10:1; Described response composite preferred version comprises 0.5wt%-8wt% water.The consumption of halogen catalyst more preferably scope is present in the described response composite for the concentration with the 5wt%-15wt% of described response composite; The mol ratio of ruthenium complex and rhodium more preferably scope is that 1:1-5:1 is present in the described response composite; Described response composite more preferably scheme for comprising 2wt%-5wt% water; The consumption of rhodium more preferably scope is present in the described response composite for the concentration with the 500ppm-2000ppm of described response composite; The consumption of iodide salt co-promoter more preferably scope is that the iodide ion concentration that produces is the concentration existence of the 5wt%-13.5wt% of response composite.The consumption preferred range of halogen catalyst exists for the concentration with the 5wt%-13.5wt% of described response composite; Described response composite preferred version is for comprising 2.01wt%-3.5wt% water.The better scope of the consumption of halogen catalyst exists for the concentration with the 5wt%-10wt% of described response composite; The better scheme of described response composite is for comprising 2.01wt%-2.95wt% water.Described response composite another one preferred version is for comprising 1.05wt%-1.99wt% water.Described response composite preferred version is for comprising the 0.5wt%-30wt% methyl acetate; The ruthenium complex preferred version is selected from [Ru (CO) 4I 2], [Ru (CO) 3I 2] 2, [Ru (CO) 2I 2] 2, [Ru (CO) 2I 2] 3, H +[Ru (CO) 3I 3] -, H +[Ru (CO) 2I 3] -, H +[Ru (CO) I 3] -, Li +[Ru (CO) 3I 3] -, Li +[Ru (CO) 2I 3] -Or Li +[Ru (CO) I 3] -In at least a.Described ruthenium complex another one preferred version is selected from Li +[RuI 3] -Or H +[RuI 3] -In at least a.The temperature of reaction preferable range is 170 ~ 210 ℃, and the reaction pressure preferable range is 2.0 ~ 6.0MPa.Temperature of reaction more preferably scope is 175 ~ 205 ℃, and reaction pressure more preferably scope is 2.1 ~ 4.1MPa.Described in the present invention in the reacting liquid composition water-content corresponding water-content in the liquid reaction composition under the simulation flash conditions when rhythmic reaction middle finger reaction proceeds to water-content corresponding under the 3wt% ritalin concentration or carries out stability experiment; Water-content in the reaction solution of continuous processing middle finger reactor the inside.
Described rhodium catalyst is selected from: rhodium metal, iodate rhodium, hydration iodate rhodium, bromination rhodium, hydration bromination rhodium, rhodium chloride, hydration rhodium chloride, [Rh (CO) 2Cl] 2, [Rh (CO) 2Br] 2, RhCl 33H 2O, Rh (OAc) 3, Rh 2O 3, H +[Rh (CO) 2I 2] -, H +[Rh (CO) 2I 4] -, Rh 4(CO) 12, Rh 6(CO) 16Wherein rhodium catalyst as Primary Catalysts, thereby claims again the rhodium Primary Catalysts in reaction.
Described iodide salt co-promoter is lithium iodide.
It is [Ru (CO) that described stablizer is selected from ruthenium complex aI b] n, M N+[Ru (CO) aI b] - nOr M N+[RuI b] - nIn at least a, wherein M is a kind of among H, Li, Na, K, Fe, Ni, Mo, Mn, Cr or the In, a is selected from the positive integer among the 1-4, b is selected from the positive integer among the 1-4, n is selected from the positive integer among the 1-4, such as [Ru (CO) 4I 2], [Ru (CO) 3I 2] 2, [Ru (CO) 2I 2] 2, [Ru (CO) 2I 2] 3, H +[Ru (CO) 3I 3] -, H +[Ru (CO) 2I 3] -, H +[Ru (CO) I 3] -, Li +[Ru (CO) 3I 3] -, Li +[Ru (CO) 2I 3] -, Li +[Ru (CO) I 3] -, Li +[RuI 3] -, H +[RuI 3] -Further preferred H +[Ru (CO) 3I 3] -, H +[Ru (CO) 2I 3] -, H +[Ru (CO) I 3] -, Li +[Ru (CO) 3I 3] -, Li +[Ru (CO) 2I 3] -, Li +[Ru (CO) I 3] -, Li +[RuI 3] -, H +[RuI 3] -The complex compound of described ruthenium comprises above compound, but is not limited to this.
Wherein, ruthenium complex is [Ru (CO) aI b] n, M N+[Ru (CO) aI b] - n, M N+[RuI b] - nAfter can preparing in advance, add rhodium-containing to, acetic acid, methyl alcohol, ritalin, methyl-iodide is in the mixed substances in reaction of iodide salt.
The active substance of rhodium catalyst catalysis methanol carbonylation is [Rh (CO) 2I 2] -, in reactor cycles water cooler, flasher or follow-up pipeline, can become [Rh (CO) 2I 4] -, [Rh (CO) I 4] - ,[RhI 4] -, and then be transformed into RhI 3Precipitation, the strainer of blocking pipe and pump, impact is normally produced.
Under high water concentration and high CO partial pressure conditions, [Rh (CO) 2I 4] -, [Rh (CO) I 4] -Can change into catalytic activity body [Rh (CO) 2I 2] -, and then suppressed RhI 3The formation of precipitation.
In liquid reaction composition because the atmosphere of low CO dividing potential drop, such as [Rh (CO) I in reactor cycles water cooler, flasher or the follow-up pipeline 4] -Generate easily [RhI 4] -But in system, there is a large amount of ruthenium complexs [Ru (CO) aI b] -Or [Ru (CO) aI b] n, it discharges certain CO easily, is conducive to keep in the whole liquid-phase system certain CO dividing potential drop; Thereby keep CO dividing potential drop certain in the whole liquid-phase system, keep [RhCOI 4] -Stability, reduce [RhI 4] -Concentration suppresses RhI 3The formation of precipitation.
Under low water condition, HI and LiI are not easy ionization, can impel poly lithium iodide [Li by adding ruthenium complex qI Q+1] -Dissociate, be conducive to the ionization of the HI of covalent linkage, the iodide ion that meanwhile dissociates out and RhI 3Generation [RhI combines 4] -, weaken or suppressed RhI 3The formation of precipitation, and can reduce the cluster of rhodium.
The present invention can increase the stability of rhodium Primary Catalysts on the one hand by add the ruthenium complex stablizer in catalystic converter system, even at lower water-content, contains [the Li that having of ruthenium complex is beneficial to poly qI Q+1] -Further dissociate, particularly [Li 5I 6] -, [Li 6I 7] -, [Li 7I 8] -, [Li 8I 9] -Deng being ionized into iodine negative ion and lithium positive ion, be conducive to stably catalyzed system; Divide at low CO and to depress, contain the existence that the ruthenium complex metal-salt is conducive to keep carbonyl iodate rhodium, be conducive to reduce or suppress [RhI 4] -Existence, in order to avoid be further converted to iodate rhodium precipitation.Can suitably improve the activity that rhodium catalyst concentration increases reaction on the other hand, particularly the reactive behavior under the low water condition; Can reduce water-gas reaction at last, improve the utilization ratio of CO, and reduce the generation of by product propionic acid.
Adopt the method for adding the ruthenium complex stablizer, the inventor is surprised to find in reactor, flasher or follow-up pipeline and also can keeping the stable of rhodium catalyst under the low water condition and still keep its reactive behavior when low water carbonylation is produced acetic acid, and reduced the unsaturated compound in the system, improved the potassium permanganate oxidation time of product, thereby reach the production cost that reduces acetic acid, the purpose of improving the quality of products has obtained preferably technique effect.
The production method of carbonylation acetic acid of the present invention can adopt rhythmic reaction mode or successive reaction mode to carry out.
Described rhythmic reaction mode, refer in the high pressure resistant zirconium material reactor that is equipped with the electric speed-sensing agitator, carry out, add in advance catalyzer and prepare the reaction solution of definite composition concentration, under temperature required and pressure, react, record at any time the instantaneous absorbed dose of CO in the reaction process, and can come stopped reaction by " Quench ", and the composition content of analytical reaction liquid.
Described rhythmic reaction mode comprises the stability experiment of rhodium catalyst or is called destructive test.Described destructive test, the stability experiment that refers to catalyzer carries out in the parallel reactor of 4 passages, the experimental solutions for preparing, under 134.0 ℃ condition, add condensing reflux and stir, the flash conditions that simulation is harsh is carried out the experiment of destructiveness precipitation, stopped heating and stirring after 12 hours, the concentration of Primary Catalysts rhodium in the solution behind the analysis destructive test.
Described successive reaction mode, referring to accompanying drawing, refer to that the promotors such as the precursor compound of the solution that contains catalytic activity Rh (I) that will prepare in advance or rhodium catalyst such as iodate rhodium or acetic acid rhodium and ruthenium complex, basic metal salt compounded of iodine and reaction soln etc. join in the carbonylation reactor 1; Then continuous carbon monoxide 30, the methyl alcohol 31 of passing into, control 170 ~ 210 ℃ of temperature of reaction (preferred 175 ~ 205 ℃), reactor pressure is controlled at 2.0 ~ 6.0MPa(preferred 2.1 ~ 4.1MPa), under the stirring of mechanical stirring 29, methyl alcohol and acetic acid reaction change into ritalin very soon, thereby methanol content is very low in the reaction system, and ritalin and the effect of basic metal salt compounded of iodine form methyl iodide, methyl iodide forms acetyliodide under the effect of rhodium catalyst, acetyliodide is hydrolyzed and forms acetic acid and hydrogen iodide.The high pressure of reactor is speeded to put tail gas 8 and is entered the high-pressure absorber (not shown), rhodium-containing Primary Catalysts, basic metal salt compounded of iodine, contain the stablizer ruthenium complex, the reaction mixture 9 of methyl iodide, acetic acid, ritalin, water enters flasher 2, and flashing pressure is 0.05～0.2Mpag.By flash distillation, the restructuring of rhodium-containing Primary Catalysts, basic metal salt compounded of iodine, ruthenium complex divides logistics 10 from flasher bottom Returning reactor 1, respectively in the catalyst recirculation pipeline and force feed prepares in advance in the flasher ruthenium complex logistics 27 and logistics 28, after the flash distillation to contain the light constituent logistics 11 such as acetic acid, ritalin, methyl iodide, water be the gas phase part, enter into washing absorption tower 3 from flasher 2 tops, and remove the part heat.Moisture logistics 12 enters from washing absorption tower 3 cats head, logistics 13 Returning reactors 1 that contain the trace rhodium Primary Catalysts, the light phase logistics 14 of washing absorption tower 3 cats head enters lightness-removing column 4, enter liquid liquid quantizer 6 from the cat head light phase logistics 16 out of lightness-removing column 4, the layering two-phase, high-density phase logistics 18 Returning reactors 1 of liquid liquid quantizer 6, part low density phase reflux stream 17 is as the phegma of lightness-removing column 4, part low density phase logistics 20 Returning reactors 1, the gaseous stream 19 of liquid liquid quantizer 6 enters low pressure absorption tower (not shown), and the tower base stream that contains the thick product of acetic acid 15 after lightness-removing column 4 separates enters treating tower 5.Treating tower overhead stream 21 makes partial reflux logistics 24 return treating tower 5 through treating tower backflash 7, light phase logistics 25 Returning reactors 1 of part, the gaseous stream 26 for the treatment of tower backflash 7 enters low pressure absorption tower (not shown), product stream 23 is from treating tower 5 middle extraction, and treating tower 5 tower reactor extraction contain the logistics 22 of high-boiling-point impurity.
Production method of the present invention, need to be to ongoing reaction system regularly or the concentration of the above each component of continuous monitoring, the concentration of catalyzer particularly, be lower than the adding value if find to measure catalyst concn, then may cause owing to reasons such as precipitation or volatilizations the loss of catalyzer, this moment can be by adding catalyzer in reaction solution.
Production method of the present invention, also further comprise refining step, be about to flash distillation logistics out and comprise that the rhodium catalyst of water, methyl-iodide, ritalin, acetic acid and trace and promotor process absorb washing tower, lights column and treating tower, finally obtain liquid product acetic acid.
The present invention is by further adding the ruthenium complex as stablizer in catalystic converter system, in reactor, flasher or follow-up pipeline so that rhodium catalyst can keep high stability under the condition of utmost point low water content, and the disadvantageous effect of energy slowing down corrosion metal pair rhodium catalyst stability, keep its reactive behavior under low water condition, thereby can less energy-consumption produce acetic acid.By absorbing washing tower micro-Primary Catalysts and the promotor that volatilizees carried out washing and recycling at last, separate with treating tower Dichlorodiphenyl Acetate product by lights column, obtain the finished product liquid acetic.
Description of drawings
Accompanying drawing 1 is the reaction unit of carbonylation acetic acid of the present invention.
1 is carbonylation reactor in the accompanying drawing 1,2 is flasher, 3 is washing absorption tower, 4 is lightness-removing column, 5 is treating tower, 6 is (lightness-removing column) liquid liquid quantizer, 7 is the treating tower backflash, 8 speed to put tail gas for high pressure, 9 is reaction mixture, 10 are rhodium-containing Primary Catalysts after the flash distillation, the basic metal salt compounded of iodine, the restructuring of ruthenium complex metal-salt divides logistics, 11 is to contain acetic acid after the flash distillation, ritalin, methyl iodide, the light constituent logistics such as water, 12 is moisture washing logistics, 13 for containing the logistics of trace rhodium catalyzer, 14 is (washing absorption Tata) light phase logistics in top, 15 for containing the tower base stream of the thick product of acetic acid at the bottom of the lightness-removing column tower, 16 is (lightness-removing column cat head) light phase logistics, 17 is liquid liquid quantizer part low density phase reflux stream, 18 is liquid liquid quantizer high-density phase (Returning reactor) logistics, 19 is the gaseous stream that liquid liquid quantizer goes to the low pressure absorption tower, 20 is the logistics of liquid liquid quantizer part low density phase, 21 is the treating tower overhead stream, 22 contain the tower reactor logistics of high-boiling-point impurity for the treating tower tower reactor, 23 is the treating tower product stream, and 24 is the logistics for the treatment of tower partial reflux, and 25 is the light phase logistics for the treatment of tower backflash part, 26 remove the gaseous stream on low pressure absorption tower for the treating tower backflash, 27 are (continuing to pass into to the catalyst recirculation pipeline) ruthenium complex logistics, and 28 are ruthenium complex logistics (continuing to pass in the flasher), and 29 is mechanical stirring, 30 is CO, and 31 is methyl alcohol.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
The general experimental technique of rhythmic reaction mode of the present invention is as follows:
In being equipped with the high pressure resistant zirconium material of the 200ml of electric speed-sensing agitator reactor, carry out, react and be external heat, zirconium material spiral coil cooling tube is arranged in the reactor.Weighing rhodium Primary Catalysts, basic metal promoter of iodized salt, ruthenium complex, ritalin, methyl iodide, water and acetic acid.Reactor is put in the initial charge that above each component consists of, then use the air in the CO replacement reaction kettle, each pressurising is to 0.3 MPa, then slowly emptying is to prevent the loss of the volatile matters such as methyl iodide, with CO 3.0MPa is arrived in the reactor pressurising again, pressurize 1h confirms that sealing is all right without leaking then slowly emptying, pressure drops to 0.6 MPa, begin to stir, heating, and by temperature in the thermocouple measurement reactor, be warmed up to 190 ℃, then pass into CO gas, keep 190 ℃ ± 1 ℃ of the interior temperature of reaction by the control external heat, by cumulative throughflow and the instantaneous delivery of mass-flow gas meter record stages.After reaction proceeds to certain phase, close the CO inlet mouth, stopped heating strengthens the spiral coil cooling tube flooding quantity, and the reactor outer wall is further used water quench, rapidly cooling.After the cooling, slowly bleed off remaining gas, and use N 2Replace three times, reactor liquid is by its composition of gas chromatographic analysis.The speed that the gas sometime that carries out with reaction absorbs is calculated instantaneous carbonylation rate, and the accumulation gas of a certain section time response consumption calculates average carbonylation rate.Suppose that equimolar CO consumes equimolar ritalin or methyl alcohol, can calculate sometime the mole number STY(mol/ (Lh) of the reactant that lower every liter instantaneous or average reaction solution per hour consumes).
The reaction solution of stability experiment simulation flash distillation; use nitrogen protection; and displace CO in the reaction solution; under nitrogen gas micro-positive pressure; laser heating 12h carries out the breaking test of catalyst stability under 134 ℃ the condition; cool to room temperature, and the content by rhodium catalyst before and after the ICP assaying reaction liquid calculate the deposition rate of rhodium catalyst.
Comparative example 1
To 200ml disposable adding acetic acid rhodium, methyl iodide, distilled water, ritalin and lithium iodide in the manometric zirconium material autoclave are housed, so that the rhodium concentration in the reaction system is 700ppm, methyl iodide 12wt%, distilled water 6wt%, ritalin 20wt%, lithium iodide 6wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa.The average STY of acetic acid of reaction is 7.5 mol/ (Lh), and in 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 1.05wt% water-content is 5.1 mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 495ppm.Reaction is finished the reaction solution nitrogen protection of rear moisture 1.05wt%, and displace the CO in the reaction solution, under nitrogen gas micro-positive pressure; laser heating 12h under 134 ℃ the condition; carry out the breaking test of catalyst stability, the rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 22.5%.
Comparative example 2
To 200ml disposable adding acetic acid rhodium, methyl iodide, distilled water, ritalin and lithium iodide in the manometric zirconium material autoclave are housed, so that the rhodium concentration in the reaction system is 700ppm, methyl iodide 12wt%, distilled water 6wt%, ritalin 20t%, lithium iodide 6wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa.The average STY of acetic acid of reaction is 7.5 mol/ (Lh), and in 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 1.05wt% water-content is 5.1mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 495ppm.The acetic acid ruthenium is joined in the rear solution of reaction end; making ruthenium concentration is 600ppm; and reaction solution nitrogen protection that will this moisture 1.05wt%; and displace CO in the reaction solution; under nitrogen gas micro-positive pressure, laser heating 12h under 134 ℃ the condition carries out the breaking test of catalyst stability; rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 43.4%.
Comparative example 3
To 200ml disposable adding acetic acid rhodium, methyl iodide, distilled water, ritalin and lithium iodide in the manometric zirconium material autoclave are housed, so that the rhodium concentration in the reaction system is 700ppm, methyl iodide 12wt%, distilled water 6wt%, ritalin 20wt%, lithium iodide 6wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa.The average STY of acetic acid of reaction is 7.5 mol/ (Lh), and in 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 1.05wt% water-content is 5.1mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 495ppm.The iodate ruthenium is joined in the solution that reacts after finishing; making ruthenium concentration is 600ppm; and reaction solution nitrogen protection that will this moisture 1.05wt%; and displace CO in the reaction solution; under nitrogen gas micro-positive pressure, laser heating 12h under 134 ℃ the condition carries out the breaking test of catalyst stability; rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 44.3%.
Embodiment 1
Ruthenium complex Li +/ H +[Ru (CO) 3I 3] -Preparation: acetic acid ruthenium or iodate ruthenium are joined in the acetum, add lithium iodide and water, HI passes into CO, at 3.0MPa, reacts 2h under 190 ℃ of conditions, separates obtaining ruthenium complex Li +/ H +[Ru (CO) 3I 3] -, infrared spectrum goes out peak position IR v(CO): about 2106.7cm -1, about 2039.0cm -1, nuclear magnetic spectrogram, the carbonyl peak position: 13CNMR (100 MHz, CDCl 3): the about 186.3ppm of δ, by Xevo G2 QTof mass spectrum, ESI/negative: 566.6020.
To 200ml disposable adding acetic acid rhodium, methyl iodide, distilled water, ritalin and lithium iodide in the manometric zirconium material autoclave are housed, so that the rhodium concentration in the reaction system is 700ppm, methyl iodide 12wt%, distilled water 6wt%, ritalin 20wt%, lithium iodide 6wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa.The average STY of acetic acid of reaction is 7.5 mol/ (Lh), and in 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 1.05wt% water-content is 5.1mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 495ppm.H with preparation +/ Li +[Ru (CO) 3I 3] -Join in the rear solution of reaction end; making ruthenium concentration is 600ppm; and the reaction solution nitrogen protection of reaction that will this moisture 1.05wt% after finishing; and displace CO in the reaction solution; under nitrogen gas micro-positive pressure, laser heating 12h under 134 ℃ the condition carries out the breaking test of catalyst stability; rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 4.9%.
Embodiment 2
Ruthenium complex Li +/ H +[Ru (CO) I 3] -, Li +/ H +[Ru (CO) 2I 3] -, Li +/ H +[Ru (CO) 3I 3] -Preparation: acetic acid ruthenium or iodate ruthenium are joined in the acetum, add lithium iodide, water, HI passes into CO, at 2.0MPa, reacts 1h under 190 ℃ of conditions, further separation obtains respectively ruthenium complex Li +/ H +[Ru (CO) I 3] -, Li +/ H +[Ru (CO) 2I 3] -, Li +/ H +[Ru (CO) 3I 3] -, Xevo G2 QTof mass spectrum, ESI/negative: 566.6020,538.6073,510.6120.
To 200ml disposable adding acetic acid rhodium, methyl iodide, distilled water, ritalin and lithium iodide in the manometric zirconium material autoclave are housed, so that the rhodium concentration in the reaction system is 700ppm, methyl iodide 12wt%, distilled water 6wt%, ritalin 20wt%, lithium iodide 6wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa.The average STY of acetic acid of reaction is 7.5 mol/ (Lh), and in 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 1.99wt% water-content is 5.1mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 495ppm.Li with preparation +/ H +[Ru (CO) I 3] -, Li +/ H +[Ru (CO) 2I 3] -, Li +/ H +[Ru (CO) 3I 3] -Join with mol ratio 1:1:5 in the rear solution of reaction end; making ruthenium concentration is 600ppm; and the reaction solution nitrogen protection of reaction solution that will this moisture 1.99wt% reaction after finishing; and displace CO in the reaction solution; under nitrogen gas micro-positive pressure, laser heating 12h under 134 ℃ the condition carries out the breaking test of catalyst stability; rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 9.8%.
Embodiment 3
Ruthenium complex [Ru (CO) 4I 2] preparation: Ru 3(CO) 12And I 2Be dissolved in the normal hexane, bathe by dry ice-propanone and be cooled to-40 ℃, and then be warmed up to gradually room temperature, desolventizing again vacuum-drying obtains a kind of brown solid, is [Ru (CO) by infrared analysis 4I 2] and [Ru (CO) 3I 2] 2Mixture, mixture is dissolved in CH 2Cl 2In, in encloses container, pass into the CO gas of 1.0 MPa, then be heated to 40 ℃, after reaction finishes, desolventizing CH 2Cl 2, obtaining yellow solid is [Ru (CO) 4I 2], IR v (CO)/cm -1(CH 2Cl 2): 2161,2106,2097,2068.
To 200ml disposable adding acetic acid rhodium, methyl iodide, distilled water, ritalin and lithium iodide in the manometric zirconium material autoclave are housed, so that the rhodium concentration in the reaction system is 700ppm, methyl iodide 12wt%, distilled water 6wt%, ritalin 20wt%, lithium iodide 6wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa.The average STY of acetic acid of reaction is 7.5 mol/ (Lh), and in 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 1.0wt% water-content is 5.1mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 495ppm.[Ru (CO) with preparation 4I 2] join in the rear solution of reaction end; making ruthenium concentration is 600ppm; and reaction solution nitrogen protection that will this moisture 1.0wt%; and displace CO in the reaction solution; under nitrogen gas micro-positive pressure, laser heating 12h under 134 ℃ the condition carries out the breaking test of catalyst stability; rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 8.0%.
Embodiment 4
Ruthenium complex [Ru (CO) 3I 2] 2Preparation: Ru 3(CO) 12And I 2Be dissolved in the normal hexane, bathe by dry ice-propanone and be cooled to-40 ℃, and then be warmed up to gradually room temperature, desolventizing again vacuum-drying obtains a kind of brown solid, is [Ru (CO) by infrared analysis 4I 2] and [Ru (CO) 3I 2] 2Mixture, mixture is dissolved in CHCl 3In, in reaction vessel, pass into nitrogen reflux 3h, after reaction finishes, desolventizing CHCl 3, obtaining the sorrel pressed powder is [Ru (CO) 3I 2] 2, IR v (CO)/cm -1(CH 2Cl 2): 2123,2067.
To 200ml disposable adding acetic acid rhodium, methyl iodide, distilled water, ritalin and lithium iodide in the manometric zirconium material autoclave are housed, so that the rhodium concentration in the reaction system is 700ppm, methyl iodide 12wt%, distilled water 6wt%, ritalin 20wt%, lithium iodide 6wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa.The average STY of acetic acid of reaction is 7.5 mol/ (Lh), and in 3wt% ritalin concentration, the average STY of the acetic acid under the 1.0wt% water-content is 5.1mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 495ppm.[the Ru (CO) of preparation 3I 2] 2Join in the rear solution of reaction end; making ruthenium concentration is 600ppm; and reaction solution nitrogen protection that will this moisture 1.0wt%; and displace CO in the reaction solution; under nitrogen gas micro-positive pressure, laser heating 12h under 134 ℃ the condition carries out the breaking test of catalyst stability; rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 10.0%.
Embodiment 5
H +/ Li +[RuI 3] -Preparation: RuI 2Be dissolved in the acetic acid, add again LiI or the HI of 2 times of equivalents, under nitrogen protection, at 100 ℃ of lower heated and stirred 3h, obtain ruthenium complex by Xevo G2 QTof mass spectrum, ESI/negative:482.6170.
To 200ml disposable adding acetic acid rhodium, methyl iodide, distilled water, ritalin and lithium iodide in the manometric zirconium material autoclave are housed, so that the rhodium concentration in the reaction system is 700ppm, methyl iodide 12wt%, distilled water 6wt%, ritalin 20wt%, lithium iodide 6wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa.The average STY of acetic acid of reaction is 7.5 mol/ (Lh), and in 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 1.05wt% water-content is 5.1mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 495ppm.With H +/ Li +[RuI 3] -Join in the rear solution of reaction end; making ruthenium concentration is 600ppm; and reaction solution nitrogen protection that will this moisture 1.05wt%; and displace CO in the reaction solution; under nitrogen gas micro-positive pressure, laser heating 12h under 134 ℃ the condition carries out the breaking test of catalyst stability; rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 11.0%.
Comparative example 1 ~ 3 and embodiment 1 ~ 5 proof add the ruthenium complexing salt and help the stable of rhodium catalyst, Li +[Ru (CO) 3I 3] -Effect is best, makes the rhodium deposition rate drop to 4.9% from 22.5%, but directly adds the acetic acid ruthenium or the iodate ruthenium has not had stabilization to rhodium, and disadvantageous effect is arranged on the contrary.
Comparative example 4
To 200ml disposable adding acetic acid rhodium, methyl iodide, distilled water, ritalin in the manometric zirconium material autoclave are housed, so that the rhodium concentration in the reaction system is 700ppm, methyl iodide 12wt%, distilled water 6wt%, ritalin 20wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa.The average STY of acetic acid of reaction is 7mol/ (Lh), and in 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 1.5wt% water-content is 5mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 550ppm.With H +/ Li +[Ru (CO) 3I 3] -Join in the rear solution of reaction end; making ruthenium concentration is 1200ppm; and reaction solution nitrogen protection that will this moisture 1.5wt%; and displace CO in the reaction solution; under nitrogen gas micro-positive pressure, laser heating 12h under 134 ℃ the condition carries out the breaking test of catalyst stability; rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 35.0%.
Embodiment 6
To 200ml disposable adding acetic acid rhodium, methyl iodide, distilled water, ritalin and lithium iodide in the manometric zirconium material autoclave are housed, so that the rhodium concentration in the reaction system is 700ppm, methyl iodide 12wt%, distilled water 6wt%, ritalin 20wt%, lithium iodide 6wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa.The average STY of acetic acid of reaction is 7.5mol/ (Lh), and in 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 1.77wt% water-content is 5.5mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 495ppm.With H +/ Li +[Ru (CO) 3I 3] -Join in the rear solution of reaction end; making ruthenium concentration is 1200ppm; and reaction solution nitrogen protection that will this moisture 1.77wt%; and displace CO in the reaction solution; under nitrogen gas micro-positive pressure, laser heating 12h under 134 ℃ the condition carries out the breaking test of catalyst stability; rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 4.4%.
Embodiment 7
To 200ml disposable adding acetic acid rhodium, methyl iodide, distilled water, ritalin and lithium iodide in the manometric zirconium material autoclave are housed, so that the rhodium concentration in the reaction system is 700ppm, methyl iodide 12wt%, distilled water 6wt%, ritalin 20wt%, lithium iodide 8wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa.The average STY of acetic acid of reaction is 8mol/ (Lh), and in 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 2.0wt% water-content is 6mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 550ppm.With H +/ Li +[Ru (CO) 3I 3] -Join in the rear solution of reaction end; making ruthenium concentration is 1200ppm; and the reaction solution nitrogen protection of reaction solution that will this moisture 2.0wt% reaction after finishing; and displace CO in the reaction solution; under nitrogen gas micro-positive pressure, laser heating 12h under 134 ℃ the condition carries out the breaking test of catalyst stability; rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 1.5%.
Embodiment 8 ~ 15 concrete operation steps are identical with embodiment 6 ~ 7, are with H all +/ Li +[Ru (CO) 3I 3] -Join in the rear solution that reaction finishes, making ruthenium concentration is 1200ppm, and difference is that the lithium iodide content that institute adds when react is different, and also difference of the water-content when simulating flash conditions and carrying out destructive test.Its experimental data such as table 1.
Table 1
Comparative example 4 proofs, in the situation of not adding lithium iodide salt (iodide ion content is lower than 3wt%), only add ruthenium complex as rhodium catalyst stablizer poor effect, and find in the experiment that whole experimental system ruthenium material reduces, condensing reflux tube wall top detects the ruthenium residue.Embodiment 8 ~ 15 proofs in embodiment 6 ~ 7 and the table 1, adding in lithium iodide and the coupling of the ruthenium carbonyl iodine complex situation stable as rhodium, rhodium deposition rate decrease, especially when lithium iodide addition 〉=8wt%, effect is better, condensing reflux tube wall top almost can't detect the ruthenium residue simultaneously, has suppressed largely the volatilization of Ruthenium carbonyl compound.
Embodiment 16
To 200ml disposable adding iodate rhodium, H in the manometric zirconium material autoclave are housed +/ Li +[Ru (CO) 3I 3] -, methyl iodide, distilled water, ritalin and lithium iodide, so that the rhodium concentration in the reaction system is 700ppm, ruthenium concentration is 1800ppm, methyl iodide 12wt%, distilled water 6wt%, ritalin 20wt%, lithium iodide 8wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa, the average STY of the acetic acid of reaction are 8.0 mol/ (Lh).In 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 1.2wt% water-content is 6.0 mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 240ppm.Reaction is finished the reaction solution nitrogen protection of rear moisture 1.2wt%, and displace the CO in the reaction solution, under nitrogen gas micro-positive pressure; laser heating 12h under 134 ℃ the condition; carry out the breaking test of catalyst stability, the rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 3.0%.
Embodiment 17
To 200ml disposable adding iodate rhodium, H in the manometric zirconium material autoclave are housed +/ Li +[Ru (CO) 3I 3] -, methyl iodide, distilled water, ritalin, lithium iodide and potassiumiodide, so that the rhodium concentration in the reaction system is 700ppm, ruthenium concentration is 2500ppm, and the concentration of potassium is 100ppm, methyl iodide 12wt%, distilled water 6wt%, ritalin 20wt%, lithium iodide 8wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa, the average STY of the acetic acid of reaction are 7.9mol/ (Lh).In 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 1.5wt% water-content is 6.2mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 245ppm.Moisture 1.5wt% reaction solution nitrogen protection after reaction finished, and displace CO in the reaction solution, under nitrogen gas micro-positive pressure; laser heating 12h under 134 ℃ the condition; carry out the breaking test of catalyst stability, the rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 0%.
Embodiment 18
To 200ml disposable adding acetic acid rhodium, H in the manometric zirconium material autoclave are housed +/ Li +[Ru (CO) 3I 3] -, methyl iodide, distilled water, ritalin and lithium iodide, so that the rhodium concentration in the reaction system is 700ppm, ruthenium concentration is 3000ppm, methyl iodide 12wt%, distilled water 5.5wt%, ritalin 20wt%, lithium iodide 8wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa, the average STY of the acetic acid of reaction are 8.5 mol/ (Lh).In 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 0.5wt% water-content is 5.3 mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 200ppm.Reaction is finished rear moisture 0.5wt% reaction solution nitrogen protection, and displace the CO in the reaction solution, under nitrogen gas micro-positive pressure; laser heating 12h under 134 ℃ the condition; carry out the breaking test of catalyst stability, the rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 0.5%.
Embodiment 19
To 200ml disposable adding acetic acid rhodium, H in the manometric zirconium material autoclave are housed +/ Li +[Ru (CO) 3I 3] -, chromium acetate, manganese acetate, methyl iodide, distilled water, ritalin, lithium iodide and sodium iodide so that the rhodium concentration in the reaction system is 500ppm, ruthenium concentration is 1200ppm, chromium concn is 300ppm, and manganese concentration is 100ppm, and na concn is 100ppm, methyl iodide 12wt%, distilled water 6wt%, ritalin 20wt%, lithium iodide 8wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa, the average STY of the acetic acid of reaction are 6.88mol/ (Lh).In 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 0.8wt% water-content is 4.7mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 250ppm.The reaction solution nitrogen protection after the moisture 0.8wt% reaction solution reaction end after the reaction end; and displace CO in the reaction solution; under nitrogen gas micro-positive pressure; laser heating 12h under 134 ℃ the condition; carry out the breaking test of catalyst stability; rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 1.1%.
Embodiment 20
To 200ml disposable adding iodate rhodium, H in the manometric zirconium material autoclave are housed +/ Li +[Ru (CO) 3I 3] -, indium acetate, methyl iodide, distilled water, ritalin, lithium iodide and sodium iodide so that the rhodium concentration in the reaction system is 900ppm, ruthenium concentration is 1500ppm, indium concentration is 800ppm, na concn is 100ppm, methyl iodide 12wt%, distilled water 6wt%, ritalin 20wt%, lithium iodide 8wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa, the average STY of the acetic acid of reaction are 9.0mol/ (Lh).In 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 1.4wt% water-content is 6.2mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 225ppm.Moisture 1.4wt% after reaction finished the reaction solution nitrogen protection, and displace CO in the reaction solution, under nitrogen gas micro-positive pressure; laser heating 12h under 134 ℃ the condition; carry out the breaking test of catalyst stability, the rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 2.5%.
Embodiment 21
To 200ml disposable adding acetic acid rhodium, H in the manometric zirconium material autoclave are housed +/ Li +[Ru (CO) 3I 3] -, Iron diacetate, methyl iodide, distilled water, ritalin and lithium iodide, so that the rhodium concentration in the reaction system is 900ppm, ruthenium concentration is 1200ppm, and concentration of iron is 800ppm, methyl iodide 12wt%, distilled water 6wt%, ritalin 20wt%, lithium iodide 8wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa, the average STY of the acetic acid of reaction are 8.80mol/ (Lh).In 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 1.0wt% water-content is 5.76mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 240ppm.The reaction solution nitrogen protection of moisture 1.0wt% after reaction finished, and displace CO in the reaction solution, under nitrogen gas micro-positive pressure; laser heating 12h under 134 ℃ the condition; carry out the breaking test of catalyst stability, the rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 4%.
Embodiment 22
To 200ml disposable adding iodate rhodium, H in the manometric zirconium material autoclave are housed +/ Li +[Ru (CO) 3I 3] -, Iron diacetate, nickel acetate, methyl iodide, distilled water, ritalin and lithium iodide so that the rhodium concentration in the reaction system is 1500ppm, ruthenium concentration is 1200ppm, concentration of iron is 1000ppm, nickel concentration is 200ppm, methyl iodide 12wt%, distilled water 6wt%, ritalin 20wt%, lithium iodide 8wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa, the average STY of the acetic acid of reaction are 9.5mol/ (Lh).In 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 1.05wt% water-content is 6.7mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 270ppm.The reaction solution nitrogen protection of moisture 1.05wt% after reaction finished, and displace CO in the reaction solution, under nitrogen gas micro-positive pressure; laser heating 12h under 134 ℃ the condition; carry out the breaking test of catalyst stability, the rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 6%.
Embodiment 23
To 200ml disposable adding iodate rhodium, H in the manometric zirconium material autoclave are housed +/ Li +[Ru (CO) 3I 3] -, Iron diacetate, nickel acetate, methyl iodide, distilled water, ritalin and lithium iodide so that the rhodium concentration in the reaction system is 1500ppm, ruthenium concentration is 1200ppm, concentration of iron is 1000ppm, nickel concentration is 200ppm, methyl iodide 12wt%, distilled water 8wt%, ritalin 20wt%, lithium iodide 8wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa, the average STY of the acetic acid of reaction are 10.5mol/ (Lh).In 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 4.0wt% water-content is 9.2mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 320ppm.The reaction solution nitrogen protection of the moisture 4.0wt% after the reaction end; and displace CO in the reaction solution; under nitrogen gas micro-positive pressure; laser heating 12h under 134 ℃ the condition; carry out the breaking test of catalyst stability; rhodium concentration before and after measuring, calculating rhodium catalyst rate rhodium catalyst deposition rate is 4%.
Embodiment 24
To 200ml disposable adding iodate rhodium, H in the manometric zirconium material autoclave are housed +/ Li +[Ru (CO) 3I 3] -, Iron diacetate, nickel acetate, methyl iodide, distilled water, ritalin and lithium iodide so that the rhodium concentration in the reaction system is 1500ppm, ruthenium concentration is 1200ppm, concentration of iron is 1000ppm, nickel concentration is 200ppm, methyl iodide 12wt%, distilled water 10wt%, ritalin 20wt%, lithium iodide 10wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa, the average STY of the acetic acid of reaction are 11.6mol/ (Lh).In 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 5.0wt% water-content is 9.9mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 350ppm.The reaction solution nitrogen protection of moisture 5.0wt% after reaction finished, and displace CO in the reaction solution, under nitrogen gas micro-positive pressure; laser heating 12h under 134 ℃ the condition; carry out the breaking test of catalyst stability, the rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 1.5%.
Embodiment 25
To 200ml disposable adding iodate rhodium, H in the manometric zirconium material autoclave are housed +/ Li +[Ru (CO) 3I 3] -, Iron diacetate, nickel acetate, methyl iodide, distilled water, ritalin and lithium iodide so that the rhodium concentration in the reaction system is 1500ppm, ruthenium concentration is 1200ppm, concentration of iron is 1000ppm, nickel concentration is 200ppm, methyl iodide 12wt%, distilled water 12wt%, ritalin 20wt%, lithium iodide 12wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa, the average STY of the acetic acid of reaction are 13mol/ (Lh).In 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 8.0wt% water-content is 10.8mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 425ppm.The reaction solution nitrogen protection of moisture 8.0wt% after reaction finished, and displace CO in the reaction solution, under nitrogen gas micro-positive pressure; laser heating 12h under 134 ℃ the condition; carry out the breaking test of catalyst stability, the rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 0%.
Embodiment 26
To 200ml disposable adding iodate rhodium, H in the manometric zirconium material autoclave are housed +/ Li +[Ru (CO) 3I 3] -, Iron diacetate, chromium acetate, methyl iodide, distilled water, ritalin, lithium iodide, sodium iodide and potassiumiodide, so that the rhodium concentration in the reaction system is 2000ppm, ruthenium concentration is 2000ppm, concentration of iron is 500ppm, chromium concn is 300ppm, na concn is 50ppm, potassium concn is 100ppm, methyl iodide 12wt%, distilled water 8wt%, ritalin 20wt%, lithium iodide 8wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa, the average STY of the acetic acid of reaction are 15mol/ (Lh).In 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 2.2wt% water-content is 13mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 245ppm.The reaction solution nitrogen protection of moisture 2.2wt% after reaction finished, and displace CO in the reaction solution, under nitrogen gas micro-positive pressure; laser heating 12h under 134 ℃ the condition; carry out the breaking test of catalyst stability, the rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 3.0%.
Embodiment 27
To 200ml disposable adding iodate rhodium, H in the manometric zirconium material autoclave are housed +/ Li +[Ru (CO) 3I 3] -, Iron diacetate, chromium acetate, methyl iodide, distilled water, ritalin, lithium iodide, sodium iodide and potassiumiodide, so that the rhodium concentration in the reaction system is 2000ppm, ruthenium concentration is 2000ppm, concentration of iron is 500ppm, chromium concn is 300ppm, na concn is 50ppm, potassium concn is 100ppm, methyl iodide 12wt%, distilled water 10wt%, ritalin 20wt%, lithium iodide 10wt%, all the other are acetate solvate, keep 190 ℃ of temperature of reaction, reaction pressure 3.0MPa, the average STY of the acetic acid of reaction are 18.5mol/ (Lh).In 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 5.4wt% water-content is 15mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 263ppm.The reaction solution nitrogen protection of moisture 5.4wt% after reaction finished, and displace CO in the reaction solution, under nitrogen gas micro-positive pressure; laser heating 12h under 134 ℃ the condition; carry out the breaking test of catalyst stability, the rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 1.0%.
Embodiment 28
To 200ml disposable adding iodate rhodium, H in the manometric zirconium material autoclave are housed +/ Li +[Ru (CO) 3I 3] -, Iron diacetate, nickel acetate, methyl iodide, distilled water, ritalin and lithium iodide so that the rhodium concentration in the reaction system is 1500ppm, ruthenium concentration is 1000ppm, concentration of iron is 1000ppm, nickel concentration is 200ppm, methyl iodide 12wt%, distilled water 7wt%, ritalin 20wt%, lithium iodide 12wt%, all the other are acetate solvate, keep 175 ℃ of temperature of reaction, reaction pressure 4.1MPa, the average STY of the acetic acid of reaction are 9.5mol/ (Lh).In 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 2.4wt% water-content is 6.8mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 355ppm.The reaction solution nitrogen protection of moisture 2.4wt% after reaction finished, and displace CO in the reaction solution, under nitrogen gas micro-positive pressure; laser heating 12h under 134 ℃ the condition; carry out the breaking test of catalyst stability, the rhodium concentration before and after measuring, calculating the rhodium catalyst deposition rate is 2.0%.
Embodiment 29
To 200ml disposable adding iodate rhodium, H in the manometric zirconium material autoclave are housed +/ Li +[Ru (CO) 3I 3] -, Iron diacetate, chromium acetate, methyl iodide, distilled water, ritalin, lithium iodide, sodium iodide and potassiumiodide, so that the rhodium concentration in the reaction system is 2000ppm, ruthenium concentration is 3000ppm, concentration of iron is 500ppm, chromium concn is 300ppm, na concn is 50ppm, potassium concn is 100ppm, methyl iodide 7wt%, distilled water 10wt%, ritalin 20wt%, lithium iodide 10wt%, all the other are acetate solvate, keep 205 ℃ of temperature of reaction, reaction pressure 2.1MPa, the average STY of the acetic acid of reaction are 13mol/ (Lh).In 3wt% ritalin concentration, the instantaneous STY of the acetic acid under the 2.8wt% water-content is 10mol/ (Lh).The content of measuring the by product propionic acid after the reaction is 263ppm.The reaction solution nitrogen protection of moisture 2.8wt% after reaction finished, and displace CO in the reaction solution, under nitrogen gas micro-positive pressure; laser heating 12h under 134 ℃ the condition carries out the breaking test of catalyst stability, the rhodium concentration before and after measuring; calculate, the rhodium catalyst deposition rate is 2.0%.
Embodiment 16 ~ 29 proofs are added the metal-salt ruthenium complex H as the rhodium catalyst stablizer +/ Li +[Ru (CO) 3I 3] -After, the reactive behavior of rhodium has certain promotion and raising, also is not subjected to simultaneously the impact of corroding metal.The stability of rhodium also improves, and further improving rhodium concentration in the situation of 2000ppm, still keeps high stability.
Successive reaction mode of the present invention is to carry out in the reaction unit of the operate continuously of the reactor that comprises belt stirrer, and reaction unit as shown in drawings.
Comparative example 5
Before test, first catalyst precursor acetic acid rhodium and lithium iodide are dissolved in the mixing solutions of acetic acid and water in advance, then with the promotor methyl iodide, lithium iodide, ritalin, water and solvent acetic acid are driven in the carbonylation reactor that volume is 10L through surge pump by interim pipeline together, and keeping the reaction solution medium is 7.0L.Reaction solution composed as follows: ritalin 3wt%, water 5wt%, methyl iodide 12wt%, rhodium concentration 700ppm, lithium iodide 10wt%, all the other are solvent acetic acid.In operating process, the temperature of carbonylation reactor 1 maintains 190 ℃, and pressure is at 3.0MPa, the methyl alcohol continuously feeding, and blast carbon monoxide by the bubbler under the agitator paddle, acetate products enters distillation system by flash distillation to be separated.Reaction is operation 650h continuously, and the instantaneous STY of acetic acid is 14mol/ (Lh), and the content of by product propionic acid is 450ppm, product potassium permanganate oxidation time 90min.By the damaed cordition of icp analysis rhodium catalyst, the density loss of rhodium about 10%.Keep other condition constant, water-content drops to 2-3wt%, moves continuously 650h, and the instantaneous STY of acetic acid is 12mol/ (Lh).The content of by product propionic acid is 350ppm, and the product potassium permanganate oxidation time is less than 60min.By the damaed cordition of icp analysis rhodium, the density loss of rhodium about 30.0%.
Embodiment 30
Before test, first iodate rhodium, lithium iodide, sodium iodide are dissolved in the mixing solutions of acetic acid and water in advance, then with the promotor methyl iodide, ritalin and water and solvent acetic acid are driven in the carbonylation reactor that volume is 10L through surge pump by interim pipeline together, and the while is pressed into H at the pipeline that the flasher catalyst recycle liquid returns reactor +/ Li +[Ru (CO) 3I 3] -, keeping the reaction solution medium is 7.0L.Reaction solution is composed as follows: ritalin 3wt%, and water 5wt%, lithium iodide 10wt%, methyl iodide 12wt%, rhodium concentration 700ppm, the concentration of ruthenium is 1000ppm, and sodium is 50ppm, and all the other are solvent acetic acid.The methyl alcohol continuously feeding, and blast carbon monoxide by the bubbler under the agitator paddle, acetate products enters distillation system by flash distillation to be separated, reaction is operation 650h continuously, generating the instantaneous STY of acetic acid is 15mol/ (Lh), the content 400ppm of by product propionic acid, the density loss of rhodium about 5%.Other condition is constant, when water-content drops to 2-3wt%, moves continuously 650h, the content 205ppm of by product propionic acid, and the product potassium permanganate oxidation time is greater than 180min.By the damaed cordition of icp analysis rhodium, the density loss of rhodium about 10.0%.
Embodiment 31
Before test, first iodate rhodium, Iron diacetate, nickel acetate, chromium acetate, lithium iodide are dissolved in the mixing solutions of acetic acid and water, then with the promotor methyl iodide, ritalin and water and solvent acetic acid are driven in the carbonylation reactor that volume is 10L through surge pump by interim pipeline together, and the while is pressed into Li at the pipeline that the flasher catalyst recycle liquid returns reactor +[Ru (CO) 3I 3] -, keeping the reaction solution medium is 7.0L.Reaction solution composed as follows: ritalin 2wt%, water 1.5wt%, lithium iodide 10wt%, methyl iodide 12wt%, rhodium concentration 700ppm, the concentration of ruthenium is 1500ppm, the concentration of iron is 1000ppm, the concentration of nickel is 350ppm, and the concentration of chromium is 100ppm, and all the other are solvent acetic acid.The methyl alcohol continuously feeding, and blast carbon monoxide by the bubbler under the agitator paddle, acetate products enters distillation system by flash distillation to be separated, reaction is operation 650h continuously, generating the instantaneous STY of acetic acid is 13mol/ (Lh), the content 250ppm of by product propionic acid, the product potassium permanganate oxidation time is greater than 120Min.By the damaed cordition of icp analysis rhodium, the density loss of rhodium about 7.0%.
Embodiment 32
Before test, first acetic acid rhodium, indium acetate, Iron diacetate, lithium iodide and potassiumiodide are dissolved in the mixing solutions of acetic acid and water in advance, then with the promotor methyl iodide, ritalin and water and solvent acetic acid are driven in the carbonylation reactor that volume is 10L through surge pump by interim pipeline together, and the while is pressed into H at the pipeline that the flasher catalyst recycle liquid returns reactor +/ Li +[Ru (CO) 3I 3] -, keeping the reaction solution medium is 7.0L.Reaction solution composed as follows: ritalin 3wt%, water 5wt%, lithium iodide 10wt%, methyl iodide 12wt%, rhodium concentration 700ppm, the concentration of ruthenium is 1500ppm, the concentration of iron is 500ppm, the concentration of indium is 2000ppm, and the concentration of potassium is 200ppm, and all the other are solvent acetic acid.The methyl alcohol continuously feeding, and blast carbon monoxide by the bubbler under the agitator paddle, acetate products enters distillation system by flash distillation to be separated, and reaction is operation 650h continuously, and generating the instantaneous STY of acetic acid is 14.5mol/ (Lh), the density loss of rhodium about 3.3%.Other condition is constant, when water-content drops to 4wt%, moves continuously 650h, the content 235ppm of by product propionic acid, and the product potassium permanganate oxidation time is greater than 180min.By the damaed cordition of icp analysis rhodium, the density loss of rhodium about 4.9%.
Embodiment 33
Before test, first iodate rhodium, Iron diacetate, nickel acetate, chromium acetate, lithium iodide are dissolved in the mixing solutions of acetic acid and water in advance, then with the promotor methyl iodide, ritalin and water and solvent acetic acid are driven in the carbonylation reactor that volume is 10L through surge pump by interim pipeline together, and the while is pressed into H at the pipeline that the flasher catalyst recycle liquid returns reactor +/ Li +[Ru (CO) 3I 3] -, keeping the reaction solution medium is 7.0L.Reaction solution composed as follows: ritalin 2wt%, water 2wt%, lithium iodide 10wt%, methyl iodide 12 wt%, rhodium concentration 1000ppm, the concentration of ruthenium is 1800ppm, the concentration of iron is 1000ppm, the concentration of nickel is 350ppm, and the concentration of chromium is 100ppm, and all the other are solvent acetic acid.The methyl alcohol continuously feeding, and blast carbon monoxide by the bubbler under the agitator paddle, acetate products enters distillation system by flash distillation to be separated, reaction is operation 650h continuously, generating the instantaneous STY of acetic acid is 20mol/ (Lh), the content 220ppm of by product propionic acid, the product potassium permanganate oxidation time is greater than 120min.By the damaed cordition of icp analysis rhodium, the density loss of rhodium about 4.5%.
Embodiment 34
Before test, first acetic acid rhodium, Iron diacetate, nickel acetate, chromium acetate, lithium iodide are dissolved in the mixing solutions of acetic acid and water in advance, then with the promotor methyl iodide, ritalin and water and solvent acetic acid are driven in the carbonylation reactor that volume is 10L through surge pump by interim pipeline together, and the while is pressed into H at the pipeline that the flasher catalyst recycle liquid returns reactor +/ Li +[Ru (CO) 3I 3] -, keeping the reaction solution medium is 7.0L.Reaction solution composed as follows: ritalin 2wt%, water 2.9wt%, lithium iodide 10wt%, methyl iodide 12wt%, rhodium concentration 1500ppm, the concentration of ruthenium is 3000ppm, the concentration of iron is 1000ppm, the concentration of nickel is 350ppm, and the concentration of chromium is 100ppm, and all the other are solvent acetic acid.The methyl alcohol continuously feeding, and blast carbon monoxide by the bubbler under the agitator paddle, acetate products enters distillation system by flash distillation to be separated, reaction is operation 650h continuously, generating the instantaneous STY of acetic acid is 28mol/ (Lh), the content 265ppm of by product propionic acid, the product potassium permanganate oxidation time is greater than 120min.By the damaed cordition of icp analysis rhodium, the density loss of rhodium about 4.0%.
Embodiment 35
Before test, first iodate rhodium, Iron diacetate, nickel acetate, chromium acetate, lithium iodide are dissolved in the mixing solutions of acetic acid and water in advance, then with the promotor methyl iodide, ritalin and water and solvent acetic acid are driven in the carbonylation reactor that volume is 10L through surge pump by interim pipeline together, and the while is pressed into H at the pipeline that the flasher catalyst recycle liquid returns reactor +/ Li +[Ru (CO) 3I 3] -, keeping the reaction solution medium is 7.0L.Reaction solution composed as follows: ritalin 2wt%, water 1.5wt%, lithium iodide 10wt%, methyl iodide 12wt%, rhodium concentration 1500ppm, the concentration of ruthenium is 2000ppm, the concentration of iron is 1000ppm, the concentration of nickel is 350ppm, and the concentration of chromium is 100ppm, and all the other are solvent acetic acid.The methyl alcohol continuously feeding, and blast carbon monoxide by the bubbler under the agitator paddle, acetate products enters distillation system by flash distillation to be separated, reaction is operation 650h continuously, generating the instantaneous STY of acetic acid is 22mol/ (Lh), the content 240ppm of by product propionic acid, the product potassium permanganate oxidation time is greater than 120min.By the damaed cordition of icp analysis rhodium, the density loss of rhodium about 7.5%.

Claims (10)

1. method for preparing acetic acid by catalyzed carbonylation reaction, described method is included under the existence of carbon monoxide and the rhodium-based catalyst systems that comprises following material, the compound that is selected from alkyl alcohol and its reactive derivatives is reacted in response composite, described alkyl alcohol is methyl alcohol, and rhodium-based catalyst systems comprises following material:
(i) rhodium;
(ii) halogen catalyst;
(iii) iodide salt co-promoter, its concentration so that the iodide ion concentration that produces greater than the 3wt% of response composite; With
(iv) be selected from the stablizer of ruthenium complex, ruthenium complex is selected from [Ru (CO) aI b] n, M N+[Ru (CO) aI b] - nOr M N+[RuI b] - nIn at least a, wherein M is a kind of among H, Li, Na, K, Fe, Ni, Mo, Mn, Cr or the In, a is selected from the positive integer among the 1-4, b is selected from the positive integer among the 1-4, n is selected from the positive integer among the 1-4;
Described response composite comprises: rhodium catalyst, halogen catalyst, ritalin, acetic acid, water, iodide salt co-promoter, and as the ruthenium complex of stablizer;
Wherein said response composite comprises 0.1wt%-14wt% water, and the mol ratio of ruthenium complex and rhodium is 0.1:1-20:1;
Wherein rhodium-based catalyst systems is illustrated at least catalyst system of 300ppm rhodium metal concentration is provided in the methanol carbonylation composition.
2. describedly according to claim 1 prepare the method for acetic acid by catalyzed carbonylation reaction, it is characterized in that rhodium is present in the described response composite with the concentration of the 300ppm-3000ppm of described response composite; Halogen catalyst is methyl-iodide; Halogen catalyst exists with the concentration of the 2wt%-20wt% of described response composite; Iodide salt co-promoter is lithium iodide; The iodide ion concentration that iodide salt co-promoter produces is that the concentration of the 4wt%-20wt% of response composite exists; The mol ratio of ruthenium complex and rhodium is 0.5:1-10:1; Described response composite comprises 0.5wt%-8wt% water.
3. describedly according to claim 2 prepare the method for acetic acid by catalyzed carbonylation reaction, it is characterized in that halogen catalyst is present in the described response composite with the concentration of the 5wt%-15wt% of described response composite; The mol ratio of ruthenium complex and rhodium is that 1:1-5:1 is present in the described response composite; Described response composite comprises 2wt%-5wt% water; Rhodium is present in the described response composite with the concentration of the 500ppm-2000ppm of described response composite; The iodide ion concentration that iodide salt co-promoter produces is that the concentration of the 5wt%-13.5wt% of response composite exists.
4. describedly according to claim 3 prepare the method for acetic acid by catalyzed carbonylation reaction, it is characterized in that halogen catalyst exists with the concentration of the 5wt%-13.5wt% of described response composite; Described response composite comprises 2.01wt%-3.5wt% water.
5. describedly according to claim 2 prepare the method for acetic acid by catalyzed carbonylation reaction, it is characterized in that described response composite comprises 1.05wt%-1.99wt% water.
6. describedly according to claim 4 prepare the method for acetic acid by catalyzed carbonylation reaction, it is characterized in that halogen catalyst exists with the concentration of the 5wt%-10wt% of described response composite; Described response composite comprises 2.01wt%-2.95wt% water.
7. describedly according to claim 1 prepare the method for acetic acid by catalyzed carbonylation reaction, it is characterized in that described response composite comprises the 0.5wt%-30wt% methyl acetate; Ruthenium complex is selected from [Ru (CO) 4I 2], [Ru (CO) 3I 2] 2, [Ru (CO) 2I 2] 2, [Ru (CO) 2I 2] 3, H +[Ru (CO) 3I 3] -, H +[Ru (CO) 2I 3] -, H +[Ru (CO) I 3] -, Li +[Ru (CO) 3I 3] -, Li +[Ru (CO) 2I 3] -Or Li +[Ru (CO) I 3] -In at least a.
8. describedly according to claim 1 prepare the method for acetic acid by catalyzed carbonylation reaction, it is characterized in that described ruthenium complex is selected from Li +[RuI 3] -Or H +[RuI 3] -In at least a.
9. describedly according to claim 1 prepare the method for acetic acid by catalyzed carbonylation reaction, it is characterized in that temperature of reaction is 170 ~ 210 ℃, reaction pressure is 2.0 ~ 6.0MPa.
10. describedly according to claim 9 prepare the method for acetic acid by catalyzed carbonylation reaction, it is characterized in that temperature of reaction is 175 ~ 205 ℃, reaction pressure is 2.1 ~ 4.1MPa.
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CN106715379A (en) * 2014-10-02 2017-05-24 国际人造丝公司 Process for producing acetic acid
CN108129289A (en) * 2016-12-01 2018-06-08 上海华谊能源化工有限公司 The preparation method of carbonylation synthesis propionic acid under a kind of ethyl alcohol low pressure
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CN107973712B (en) * 2017-11-28 2023-09-12 天津渤化永利化工股份有限公司 System and method for improving propionic acid yield
CN114478149A (en) * 2022-01-18 2022-05-13 吉林化工学院 Carboxylic acid compound and preparation method thereof
CN114478149B (en) * 2022-01-18 2023-09-15 吉林化工学院 Carboxylic acid compound and preparation method thereof

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