CN103772197A - Production method of catalyst dilution loading oxalate - Google Patents
Production method of catalyst dilution loading oxalate Download PDFInfo
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- CN103772197A CN103772197A CN201210412539.9A CN201210412539A CN103772197A CN 103772197 A CN103772197 A CN 103772197A CN 201210412539 A CN201210412539 A CN 201210412539A CN 103772197 A CN103772197 A CN 103772197A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
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Abstract
The invention relates to a production method of catalyst dilution loading oxalate, which mainly solves the problems of low raw material per-pass conversion and low oxalate selectivity in the prior art. With the adoption of the technical scheme that CO and nitrite at a mole ratio of (1-5):1 are introduced to a fixed bed reactor as raw materials at the feed temperature of 60-160 DEG C, and perform contact reaction with a palladium-bearing catalyst at the pressure of 0-1.5MPa, heat generated by the reaction is removed by heat exchange timely, the reactor comprises at least two catalyst bed layers, the height of each catalyst bed layer is Hn, Hn/H1 is equal to (1-5):1 by taking the height H1 of the first bed layer at the upper part as a reference, a volume ratio of inert filler without catalyst activity to a catalyst is (0-4):1, and the volume ratios of the catalyst in the bed layers from the top down are gradually increased, the problems are better solved, and the method can be used for industrial production of oxalate.
Description
Technical field
The present invention relates to a kind of barkite production method of catalyst dilution filling, in particular, relate to a kind of vapor phase process CO and in the calandria type fixed bed reactor of catalyst dilution filling, react the method for producing dimethyl oxalate or oxalic acid diethyl ester with methyl nitrite or ethyl nitrite.
Background technology
Barkite is important industrial chemicals, can be used for preparing intermediate, plastics promotor and the solvent etc. of oxalic acid, ethylene glycol, carbonic ether, oxamide, medicine and dyestuff.
The production line of tradition barkite is that the method that adopts oxalic acid and alcohol to dewater take toluene as dewatering agent esterification is produced, and its production process is long, energy consumption is high, seriously polluted, cost is high, suddenly waits to find new operational path.Opened up the new important channel of C1 chemical production barkite by CO and nitrous acid ester synthesis of oxalic ester by gaseous catalysis.Since the eighties, report successively the synthetic new development of barkite abroad.Japanese Patent JP8242656 openly speciallys permit communique and has reported and adopt platinum metals loaded catalyst to carry out the technical process of CO and methyl nitrite synthesizing dimethyl oxalate, and the space-time yield of catalyzer is 432g/L.h, and through 480 hours successive reactions, yield did not reduce.There are again subsequently many patents in succession to report and in catalyst component, add respectively Mo, Ni, Ti, Fe, Ga, Cu, Na
2o and SiO
2deng the catalyzer of auxiliary agent composition, be applied in the technique of CO and nitrous acid ester gas-phase dimethyloxalate synthesis, oxalic acid diethyl ester and oxalic acid diisopropyl ester, but space-time yield is still lower.Pd/Al as disclosed in U.S. Pat P4334433
2o
3and Pd-Ni/Al
2o
3catalyzer, at normal pressure, 110 ℃ and air speed 2000h
-1, initial feed gas composition: CH
3oNO:15%, CO:20%, CH
3oH:15%, NO:3%, N
2: 47%(volumetric concentration, below the concentration of all gas all refer to volumetric concentration) condition under, dimethyl oxalate space-time yield 400 g/L.h, reach 95% by the selectivity of CO oxalic dimethyl ester; To synthesis of diethyl oxalate employing, Pd-Mo/Al
2o
3catalyzer, at normal pressure, 120
oc and air speed 3900h
-1, initial feed gas composition: C
2h
5oNO:8%, CO:60% and N
2: under 32% condition, oxalic acid diethyl ester space-time yield is 550 g/L.h, by C
2h
5the selectivity of ONO oxalic diethyl ester is 90.5%.The disclosed Pd-Ti/Al of USP4507494
2o
3catalyzer, at 0.24MPa, 115
oc～120
oCwith air speed 3000h
-1, initial feed gas composition: CH
3oNO:10%, CO:20%, CH
3oH:4%, NO:3%, N
2: under 63% condition, successive reaction 950 hours, dimethyl oxalate space-time yield 429～462 g/L.h, can be reached more than 95% by the selectivity of CO oxalic dimethyl ester.
Prepare the research and development of barkite Technology along with Oxidation of Carbon Monoxide coupling method in the world, domestic many research institutions have also carried out research work to this field.At present, become the important research topic of domestic one-carbon chemical and organic chemical industry field by Oxidation of Carbon Monoxide coupling method synthesis of oxalate.Successively there are the organic institute in Chinese Academy of Sciences Chengdu, Fujian thing structure institute, southwestern chemical research institute, one carbonizer National Key Laboratory of University Of Tianjin, Nankai University, Zhejiang University, East China University of Science, Shanghai Hua Yi group, Deng Duojia research institution of Shanghai Petroleum Chemical Engineering Institute of China Petrochemical Industry and research institutions to be devoted to the work such as catalyst preparation and process exploitation in this field, and obtained greater advance.
Chinese patent 96109811.2 discloses a kind of oxalate by gas phase CO link-coupled regeneration catalyzing circulation diethyl ester, and CO, under ethyl nitrite is participated in, reacts for self-closing circulating process, and employing catalyzer is Pd-Fe/Al
2o
3load type double-metal solid catalyst, temperature of reaction is 100～120
oc, pressure is 0.1MPa, oxalic acid diethyl ester space-time yield is up to 780 g/L.h.
Chinese patent 200710060003.4 discloses a kind of method of CO preparing diethyl oxalate by coupling, adopt vapor phase process, under the catalysis of bimetal supported catalyst, CO gas enters coupler reactor with the ethyl nitrite from regeneration reactor through mixing preheating, coupling oxalic diethyl ester crude product, reaction is self-closing circulating process, the present invention is on the basis of lab scale research in early stage, carry out take industrial production as background, continuous operation examination is amplified in the mould examination and the pilot scale that have completed under industrial operation condition.The oxalic acid diethyl ester space-time yield that reaction obtains is 500 g/L.h, and oxalic acid diethyl ester selectivity is more than 96%.
Although numerous domestic and international research institutions, obtain compared with much progress technically, but the technology of disclosed report focuses mostly on aspect the catalyzer and technique research and development of CO coupling producing oxalic ester, suppressor mode to hot spots in adopted reactor types and reactor is seldom reported, exist raw material per pass conversion low, the open defect that barkite selectivity is low.
As everyone knows, the reaction of CO coupling synthesis of oxalate is strong exothermal reaction.For strong exothermic process, heat must be removed by reactant or thermal barrier timely and effectively, to avoid occurring the generation of sintering of catalyst accident and some side reactions, adopts at present common calandria type fixed bed reactor both at home and abroad more.But, at inlet section, because reactant concn is high, thermal discharge is large, and temperature of charge will sharply rise, but along with the consumption of reactant, rate of heat release reduces gradually, and temperature of charge can decline again gradually, occurs temperature vertex---focus in beds, when rising slightly, the temperature of heat-eliminating medium may cause bed temperature significantly to raise, very easily cause beds temperature runaway, this must be unfavorable to catalyzer, affects reaction preference and quality product.Thereby, for the large reaction of heat effect, in adopting heat-eliminating medium to remove reaction heat effectively in time, adopt the inert filler dilute catalyst without any catalyst activity, to reduce the reaction heat of unit volume bed, thereby effectively controlling temperature of reaction, and prevent undesirable hot spots, is also effective measure.In Chinese patent 94116548.5, disclose the filling method of dilute catalyst in a kind of multistage laminar fixed-bed reactor, but this filling method is also only applicable to laminar fixed-bed reactor.Thereby, how more effectively to make CO coupling catalyst react under optimized operational condition, give full play to their catalytic performance, effectively control temperature of reaction interval, prevent that undesirable hot spots from occurring, increase the selectivity of object product, be still CO gas phase coupling and produce the emphasis of barkite technical study and the focus of concern.
Summary of the invention
Technical problem to be solved by this invention is that the raw material per pass conversion existing in conventional art is low, the problem that barkite selectivity is low, the barkite production method that a kind of new catalyst dilution filling is provided, it is high that the method has feed stock conversion, the feature that barkite selectivity is good.
For solving the problems of the technologies described above, the present invention adopts technical scheme as follows: a kind of barkite production method of catalyst dilution filling, introduce fixed-bed reactor take CO and nitrous acid ester as raw material, be 1～5:1 in the mol ratio of CO and nitrous acid ester, feeding temperature is 60～160 ℃, pressure be under the condition of 0～1.5MPa with palladium-containing catalyst contact reacts oxalic ester, the heat that reaction produces is shifted out in time by heat exchange, in described reactor, comprise at least two-stage catalytic agent bed, every section of catalyst bed layer height is H
n, with top first paragraph bed height H
1for benchmark, H
n/ H
1=1 ~ 5:1, and the inert filler without any catalyst activity is filled in take volume ratio with catalyzer in each section of beds after 0 ~ 4:1 ratio is fully mixed, every section of shared volume ratio of bed inner catalyst increases gradually from top to bottom.
In technique scheme, entering the CO of reactor and the mol ratio of nitrous acid ester is 1.2～4:1, and feeding temperature is 70～140 ℃, and pressure is 0.1～1.0MPa.In reactor, comprise at least two-stage catalytic agent bed, each section of catalyst bed layer height is H
n, with top first paragraph beds height H
1for benchmark, H
n/ H
1=1 ~ 3:1.Inert filler without any catalyst activity is filled in after 0 ~ 2:1 ratio is fully mixed take volume ratio in each section of beds with catalyzer, and preferred volume ratio scope is 0 ~ 1:1, and every section of shared volume ratio of bed inner catalyst increases gradually from top to bottom.The active ingredient of the catalyzer in every section of beds all contains palladium, active ingredient is selected from palladium metal, the oxide compound of palladium or its mixture, carrier is selected from silicon oxide, at least one in aluminum oxide, auxiliary agent is selected from nickel, titanium, at least one in cerium or cobalt metal or its metal oxide, take carrier as benchmark, with the weighing scale of simple substance palladium, be selected from palladium metal, the oxide compound of palladium or the consumption of its mixture are that weight content is 0.1～5%, preferable range is 0.15～2%, with the weighing scale of auxiliary agent elemental metals, the consumption that is selected from the oxide compound of promoter metal or promoter metal is that weight content is 0～2%, preferable range is 0～1%.Fixed-bed reactor are tubular fixed-bed reactor, and catalyst loading is in pipe, and the heat that reaction produces is shifted out in time by the heat-eliminating medium heat exchange outside pipe.Fixed-bed reactor are tubular fixed-bed reactor, and catalyst loading is outside pipe, and the heat that reaction produces is shifted out in time by the heat-eliminating medium heat exchange in pipe.Comprise at least one in inertia aluminum oxide, inertia silicon oxide without the inert filler of any catalyst activity.Nitrous acid ester is selected from ethyl nitrite or methyl nitrite.
As everyone knows, the reaction of CO preparing oxalate by coupling reaction is thermopositive reaction.According to reacting dynamics characteristic, reactant concn is higher, and speed of response is faster, and reaction conversion ratio is higher, and beds temperature rise is also higher.In CO and nitrous acid ester coupling reaction process, in the time adopting without the filling scheme of inert filler dilute catalyst, because inlet section reactant concn is the highest, speed of reaction is very fast, in unit time, thermal discharge is larger, and concentrate heat release must cause the local temperature rise that catalyzer is higher, thereby make reactor have hot spots, when rising slightly, the temperature of heat-eliminating medium may cause bed temperature significantly to raise, very easily cause beds temperature runaway, this must be unfavorable to catalyzer, affects reaction preference and quality product.But along with the consumption of reactant, reactant concn reduces gradually, and rate of heat release reduces gradually, temperature of charge can decline again gradually, the catalyzer of bottom can not be given full play to katalysis, even can cause undesirable side reaction and occur, and affects the selectivity of object product.Research also shows, in CO and nitrous acid ester coupling reaction process, nitrous acid ester decomposes is the major cause that causes reacting object product barkite elective reduction, and the decomposes of nitrous acid ester and the temperature of reactor bed are closely-related, it is higher that the higher nitrous acid ester of temperature decomposes probability.Thereby, in the reaction process of CO preparing oxalate by coupling reaction, reaction heat must be shifted out to reduce temperature of reaction in time, and in coupling reaction process, also should avoid concentrations heat release to cause local temperature rise too high as far as possible, thereby guarantee the performance of catalyst action and the utilization ratio of catalyzer, guarantee the transformation efficiency of raw material and the selectivity of object product barkite.Although calandria type fixed bed reactor can be removed a large amount of reaction heat to a certain extent by heat-eliminating medium at present, but still cannot avoid because inlet section reactant concn is higher, the interior epimere beds temperature rise of tubulation is higher, exists hot spots to the disadvantageous shortcoming of catalyzer at beds epimere.Technical solution of the present invention is fully being studied on the basis of CO linked reaction feature and methyl nitrite decomposes mechanism, proposed by heat-eliminating medium timely and effective remove reaction heat in, the technology that adopts different ratios inert filler and CO coupling catalyst to load in mixture along Flow of Goods and Materials direction in reactor, all increase gradually along the height of the catalyst content in Flow of Goods and Materials direction beds and beds from top to bottom, desired catalyzer reasonable volume and reasonable reaction time in the case of the reduction gradually along Flow of Goods and Materials orienting response substrate concentration are guaranteed, and catalyzer is after dilution, rate of heat release is controlled, avoided because of inlet section reactant concn too high, speed of reaction is too fast, thermal discharge beds local temperature rise large and that cause is higher, make the interior temperature distribution of beds mild, temperature of reaction is the optimal reaction temperature district of each tiny area in requiring in reactor tubulation, decomposes and the beds temperature runaway of the nitrous acid ester causing because of beds local superheating are avoided, inactivation, improve the transformation efficiency of raw material, increase the selectivity of object product barkite, and take full advantage of catalyzer.
Adopting technical scheme of the present invention, introduce fixed-bed reactor take CO and nitrous acid ester as raw material, is 1.2～4:1 in the mol ratio of CO and nitrous acid ester, and feeding temperature is 70
oc～140
oc, under the condition that pressure is 0～1.0MPa, with catalyzer contact reacts oxalic ester, the heat that reaction produces is shifted out in time by heat exchange, comprises at least two-stage catalytic agent bed in reactor, and every section of catalyst bed layer height is H
n, with top first paragraph bed height H
1for benchmark, H
n/ H
1=1 ~ 3:1, and the inert filler without any catalyst activity is filled in after 0 ~ 2:1 ratio is fully mixed take volume ratio in each section of beds with catalyzer, every section of shared volume ratio of bed inner catalyst increases gradually from top to bottom, the carrier of every section of palladium-containing catalyst is selected from silicon oxide, at least one in aluminum oxide, active ingredient is selected from the oxide compound of palladium, auxiliary agent is selected from least one in the oxide compound of nickel or the oxide compound of cerium, take carrier as benchmark, with the weighing scale of simple substance palladium, the consumption that is selected from the oxide compound of palladium is that weight content is 0.15%～2%, with the weighing scale of auxiliary agent elemental metals, the consumption that is selected from the oxide compound of promoter metal is that weight content is 0～1%, inert filler comprises the aluminum oxide of inertia, at least one in silicon oxide.Under these conditions, the per pass conversion of nitrous acid ester reaches as high as and is greater than 85%, and the selectivity of barkite reaches as high as and is greater than 99%, has obtained good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
The reactor of CO coupling production dimethyl oxalate is tubulation fixed-bed reactor, tubulation apparatus with catalyst inside, and tubulation is outward heat-eliminating medium.Entering the CO of reactor and the mol ratio of methyl nitrite is 1.5:1, and feeding temperature is 100 ℃, and pressure is 0.3MPa, and catalyzer is Pd/Al
2o
3catalyzer, only supported palladium, with the weighing scale of simple substance palladium, the consumption that is selected from the oxide compound of palladium is that weight content is 0.8%.In tubulation, comprise two-stage catalytic agent bed, upper and lower beds height H
2/ H
1=2:1, epimere beds is the uniform mixture of catalyzer and inertia alumina supporter, the volume ratio of inertia alumina supporter and catalyzer is 0.5:1, only contains catalyzer in lower section catalyst bed.In the above conditions, by the present invention, to CO coupling synthesizing dimethyl oxalate, reaction designs, and the per pass conversion of methyl nitrite is 85.6%, and the selectivity of dimethyl oxalate is 98.9%.
[embodiment 2]
The reactor of CO coupling production dimethyl oxalate is tubular fixed-bed reactor, manages exterior catalyzer, in pipe, is heat-eliminating medium, and the form of reactor is with Chinese patent 200910057857.6.Entering the CO of reactor and the mol ratio of methyl nitrite is 1.2:1, and feeding temperature is 70 ℃, and pressure is 0.1MPa, and catalyzer is Pd-Ti/Al
2o
3catalyzer, with the weighing scale of simple substance palladium, the consumption that is selected from the oxide compound of palladium metal and palladium is that weight content is 2%, and auxiliary agent Ti is with the weighing scale of simple substance titanium, and the consumption that is selected from titanyl compound is that weight content is 0.2%.In tubulation, comprise three sections of beds, the aspect ratio of three sections of beds is H
3/ H
2/ H
1=3:1.5:1, first paragraph beds is the uniform mixture of catalyzer and inertia alumina supporter, the volume ratio of inertia alumina supporter and catalyzer is 2:1, second segment beds is the uniform mixture of catalyzer and inertia alumina supporter, the volume ratio of inertia alumina supporter and catalyzer is 0.8:1, in the 3rd section of beds, only contains catalyzer.In the above conditions, by the present invention, to CO coupling synthesizing dimethyl oxalate, reaction designs, and the per pass conversion of methyl nitrite is 76%, and the selectivity of dimethyl oxalate is 97.8%.
[embodiment 3]
The reactor of CO coupling production oxalic acid diethyl ester is tubulation fixed-bed reactor, tubulation apparatus with catalyst inside, and tubulation is outward heat-eliminating medium.Entering the CO of reactor and the mol ratio of ethyl nitrite is 5:1, and feeding temperature is 140 ℃, and pressure is 1.0MPa, and catalyzer is Pd-Ni/(Al
2o
3+ SiO
2) catalyzer, with the weighing scale of simple substance palladium, the consumption that is selected from the oxide compound of palladium is that weight content is 0.15%, auxiliary agent Ni is with the weighing scale of elemental nickel, the consumption that is selected from metallic nickel is that weight content is 2%, comprises three sections of beds in tubulation, and the aspect ratio of three sections of beds is H
3/ H
2/ H
1=5:3:1, first paragraph beds is the uniform mixture of catalyzer and inertia aluminum oxide and inertia aktivton carrier, the volume ratio of inert filler and catalyzer is 3:1, second segment beds is the uniform mixture of catalyzer and inertia alumina supporter, the volume ratio of inertia alumina supporter and catalyzer is 2:1, in the 3rd section of beds, only contains catalyzer.In the above conditions, by the present invention, to CO coupling-synthesizing diethyl oxalate, reaction designs, and the per pass conversion of ethyl nitrite is 79.3%, and the selectivity of oxalic acid diethyl ester is 97.9%.
[embodiment 4]
The reactor of CO coupling production dimethyl oxalate is tubulation fixed-bed reactor, tubulation apparatus with catalyst inside, and tubulation is outward heat-eliminating medium.Entering the CO of reactor and the mol ratio of methyl nitrite is 2:1, and feeding temperature is 100 ℃, and pressure is 0.5MPa, and catalyzer is Pd-Co/Al
2o
3catalyzer, with the weighing scale of simple substance palladium, the consumption that is selected from the oxide compound of palladium metal and palladium is that weight content is 0.5%, auxiliary agent Co is with the weighing scale of simple substance cobalt, the consumption that is selected from the oxide compound of cobalt is that weight content is 0.8%, in tubulation, comprise three sections of beds, the aspect ratio of three sections of beds is H
3/ H
2/ H
1=2:1.5:1, first paragraph beds is the uniform mixture of catalyzer and inertia silica support, the volume ratio of inertia silica support and catalyzer is 1.2:1, the uniform mixture of second segment beds catalyzer and inertia alumina supporter, the volume ratio of inertia alumina supporter and catalyzer is 0.4:1, and the 3rd section of beds only contains catalyzer.In the above conditions, by the present invention, to CO coupling synthesizing dimethyl oxalate, reaction designs, and the per pass conversion of dimethyl oxalate is 87.3%, and the selectivity of dimethyl oxalate is 99.2%.
[embodiment 5]
The reactor of CO coupling production dimethyl oxalate is tubulation fixed-bed reactor, tubulation apparatus with catalyst inside, and tubulation is outward heat-eliminating medium.Entering the CO of reactor and the mol ratio of methyl nitrite is 3:1, and feeding temperature is 90 ℃, and pressure is 0.35MPa, and catalyzer is Pd-Ce/Al
2o
3catalyzer, with the weighing scale of simple substance palladium, the consumption that is selected from the oxide compound of palladium metal and palladium is that weight content is 0.6%, auxiliary agent Ce is with the weighing scale of simple substance cerium, the consumption of the oxide compound of selected from cerium is that weight content is 0.7%, comprises two-stage catalytic agent bed in tubulation, upper and lower beds height H
2/ H
1=2.5:1, epimere beds is the uniform mixture of catalyzer and inertia alumina supporter, and the volume ratio of property alumina supporter and catalyzer is 0.3:1, and lower section catalyst bed only contains catalyzer.In the above conditions, by the present invention, to CO coupling synthesizing dimethyl oxalate, reaction designs, and the per pass conversion of methyl nitrite is 86.8%, and the selectivity of dimethyl oxalate is 99.1%.
[embodiment 6]
The reactor of CO coupling production oxalic acid diethyl ester is tubulation fixed-bed reactor, tubulation apparatus with catalyst inside, and tubulation is outward heat-eliminating medium.Entering the CO of reactor and the mol ratio of ethyl nitrite is 4:1, and feeding temperature is 110 ℃, and pressure is 0.5MPa, and catalyzer is Pd-Ni/(Al
2o
3+ SiO
2) catalyzer, with the weighing scale of simple substance palladium, the consumption that is selected from the oxide compound of palladium is that weight content is 0.6%, auxiliary agent Ni is with the weighing scale of elemental nickel, the consumption that is selected from the oxide compound of nickel is that weight content is 0.3%, comprises three sections of beds in tubulation, and the aspect ratio of three sections of beds is H
3/ H
2/ H
1=1.5:1.2:1, first paragraph beds is the uniform mixture of catalyzer and inertia aluminum oxide and inertia aktivton carrier, the volume ratio of inert filler carrier and catalyzer is 1:1, second segment beds is the uniform mixture of catalyzer and inertia alumina supporter, the volume ratio of inertia alumina supporter and catalyzer is 0.5:1, in the 3rd section of beds, only contains catalyzer.In the above conditions, by the present invention, to CO coupling-synthesizing diethyl oxalate, reaction designs, and the per pass conversion of oxalic acid diethyl ester is 85.5%, and the selectivity of oxalic acid diethyl ester is 98.7%.
[comparative example 1]
According to [embodiment 6] identical condition and reaction raw materials, loading catalyst only in reactor tubulation, does not adopt inert filler dilution, and the per pass conversion of methyl nitrite is 66%, and the selectivity of dimethyl oxalate is 94.8%.
[comparative example 2]
According to [embodiment 6] identical condition and reaction raw materials, loading catalyst only in reactor tubulation, does not adopt inert filler dilution, and the per pass conversion of ethyl nitrite is 67.5%, and the selectivity of oxalic acid diethyl ester is 95.2%.
Claims (10)
1. the barkite production method of a catalyst dilution filling, introduce fixed-bed reactor take CO and nitrous acid ester as raw material, be 1～5:1 in the mol ratio of CO and nitrous acid ester, feeding temperature is 60～160 ℃, pressure be under the condition of 0～1.5MPa with palladium-containing catalyst contact reacts oxalic ester, the heat that reaction produces is shifted out in time by heat exchange; In described reactor, comprise at least two-stage catalytic agent bed, every section of catalyst bed layer height is H
n, with top first paragraph bed height H
1for benchmark, H
n/ H
1=1 ~ 5:1, and the inert filler without any catalyst activity is filled in take volume ratio with catalyzer in each section of beds after 0 ~ 4:1 ratio is fully mixed, every section of shared volume ratio of bed inner catalyst increases gradually from top to bottom.
2. the barkite production method of catalyst dilution filling according to claim 1, it is characterized in that entering the CO of reactor and the mol ratio of nitrous acid ester is 1.2～4:1, and feeding temperature is 70～140 ℃, and pressure is 0.1～1.0MPa.
3. the barkite production method of catalyst dilution filling according to claim 1, is characterized in that comprising at least two-stage catalytic agent bed in reactor, and each section of catalyst bed layer height is H
n, with top first paragraph beds height H
1for benchmark, H
n/ H
1=1 ~ 3:1.
4. the barkite production method of catalyst dilution filling according to claim 1, it is characterized in that the inert filler without any catalyst activity after 0 ~ 2:1 ratio is fully mixed, to fill in take volume ratio with catalyzer in each section of beds, every section of shared volume ratio of bed inner catalyst increases gradually from top to bottom.
5. the barkite production method of catalyst dilution filling according to claim 1, the active ingredient that it is characterized in that the catalyzer in every section of beds all contains palladium, active ingredient is selected from palladium metal, the oxide compound of palladium or its mixture, carrier is selected from silicon oxide, at least one in aluminum oxide, auxiliary agent is selected from nickel, titanium, at least one in cerium or cobalt metal or its metal oxide, take carrier as benchmark, with the weighing scale of simple substance palladium, be selected from palladium metal, the oxide compound of palladium or the consumption of its mixture are that weight content is 0.1～5%, with the weighing scale of auxiliary agent elemental metals, the consumption that is selected from the oxide compound of promoter metal or promoter metal is that weight content is 0～2%.
6. the barkite production method of catalyst dilution filling according to claim 5, the active ingredient that it is characterized in that the catalyzer in every section of beds all contains palladium, active ingredient is selected from palladium metal, the oxide compound of palladium or its mixture, carrier is selected from silicon oxide, at least one in aluminum oxide, auxiliary agent is selected from nickel, titanium, at least one in cerium or cobalt metal or its metal oxide, take carrier as benchmark, with the weighing scale of simple substance palladium, the consumption that is selected from the oxide compound of palladium is that weight content is 0.15～2%, with the weighing scale of auxiliary agent elemental metals, the consumption that is selected from the oxide compound of promoter metal is that weight content is 0～1%.
7. the barkite production method of catalyst dilution filling according to claim 1, is characterized in that comprising at least one in inertia aluminum oxide, inertia silicon oxide without the inert filler of any catalyst activity.
8. the barkite production method of catalyst dilution filling according to claim 1, is characterized in that fixed-bed reactor are tubular fixed-bed reactor, and catalyst loading is in pipe, and the heat that reaction produces is shifted out in time by the heat-eliminating medium heat exchange outside pipe.
9. the barkite production method of catalyst dilution filling according to claim 1, is characterized in that fixed-bed reactor are tubular fixed-bed reactor, and catalyst loading is outside pipe, and the heat that reaction produces is shifted out in time by the heat-eliminating medium heat exchange in pipe.
10. the barkite production method of catalyst dilution filling according to claim 1, is characterized in that nitrous acid ester is selected from ethyl nitrite or methyl nitrite.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845404A (en) * | 2021-09-30 | 2021-12-28 | 中国石油化工股份有限公司 | Method for preparing hydrogenated bisphenol A by catalytic hydrogenation of bisphenol A |
| CN116492935A (en) * | 2023-04-27 | 2023-07-28 | 四川正达凯新材料有限公司 | Hydrogenation catalyst filling method |
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|---|---|---|---|---|
| CN1132112A (en) * | 1994-10-06 | 1996-10-02 | 中国石油化工总公司 | Non-contour filling method of catalyst |
| CN102219682A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for preparing oxalic ester by CO coupling |
| CN102219679A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for producing oxalic acid ester through CO gas phase coupling |
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| CN113845404A (en) * | 2021-09-30 | 2021-12-28 | 中国石油化工股份有限公司 | Method for preparing hydrogenated bisphenol A by catalytic hydrogenation of bisphenol A |
| CN116492935A (en) * | 2023-04-27 | 2023-07-28 | 四川正达凯新材料有限公司 | Hydrogenation catalyst filling method |
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