CN103901132A - Device and method for evaluating catalyst during preparation of oxalate through CO gas phase oxidative coupling - Google Patents
Device and method for evaluating catalyst during preparation of oxalate through CO gas phase oxidative coupling Download PDFInfo
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Abstract
The invention discloses a device for evaluating a catalyst during preparation of oxalate through CO gas phase oxidative coupling and a method for evaluating the catalyst by using the device. The device comprises a gas control pipeline system (1), a fixed bed reaction system (2), an insulation pipeline (3), a multi-ported valve system (4), a dual-channel gas chromatography system (5) and a product absorbing tank (6), wherein the gas control pipeline system (1) comprises three paths of gas control pipelines, each path comprises a gas conveying pipeline, a pressure stabilizing valve (7), a pressure meter (11), a current stabilizing valve (8), a quality and flow controller (9) and a switch valve (10) which are sequentially connected, the three paths of gas control pipelines are integrated into a path through a straight cross joint, and a master pressure meter (11') is arranged on the integrated pipeline. According to the device, all-component real-time synchronous analysis of raw materials and products can be realized through one dual-channel gas chromatography with the multi-ported valve system, the analysis efficiency is high, data is accurate and reliable, and the funding is less.
Description
Technical field
The invention belongs to catalyst development field of engineering technology, be specifically related to a kind of catalyst test apparatus and evaluating catalyst method of CO gaseous oxidation preparing oxalate coupling reaction.
Background technology
Ethylene glycol is a kind of extremely important, strategic large chemical industry base stock.The annual demand of China is more than 1,000 ten thousand tons, and production capacity is only more than 300 ten thousand tons, and imbalance between supply and demand is very outstanding, needs in a large number import.Coal-ethylene glycol technology utilizes coal resources to be significant for imbalance between supply and demand and the high-efficiency cleaning of alleviating China's ethylene glycol.CO gaseous oxidation preparing oxalate coupling reaction is in coal-ethylene glycol technology, to realize the committed step that inorganics CO transforms to organism oxalate.
The reaction principle of CO gaseous oxidation preparing oxalate coupling reaction is as follows:
2CO+2RONO=(ROCO)
2+ 2NO (R=CH
3-or CH
3cH
2-)
Raw material is CO and the nitrites of gaseous state, and principal product is organism oxalate, and accessory substance is dimethyl carbonate, methyl acetate, methyl formate and methyl alcohol.
The boiling point of dimethyl oxalate is 174 DEG C, and fusing point is 54 DEG C, is solid under room temperature.
The boiling point of diethy-aceto oxalate is 185 DEG C, and fusing point is-4l DEG C, is liquid under room temperature.
Prior art is by condensation, collection of products to be got off, and then calculates the selectivity of product by the sample introduction analysis of having an injection, and the direct air inlet analysis of hplc of uncondensed gas calculates the conversion ratio of raw material CO.
Mainly there is the problem of following three aspects:: l in prior art, collect product and the sample introduction analysis efficiency of having an injection low, need special messenger to wait in device limit timing sampling analysis; 2, product analysis is asynchronous with unstrpped gas analysis, causes analysis data not rigorous; 3, need to be equipped with two gas chromatographies, one configures flame ionization ditector and capillary column, for analyzing organic product, and another configuration thermal conductivity detector (TCD) and packed column, for analyzing uncondensed gas, fund input is larger.
Summary of the invention
The problem existing for catalyst test apparatus and the evaluating catalyst method of existing CO gaseous oxidation preparing oxalate coupling reaction, the invention provides catalyst test apparatus and the evaluating catalyst method of the CO gaseous oxidation preparing oxalate coupling reaction that a kind of full constituent real-time synchronization analyzes, solved the technical matters existing in existing evaluating apparatus and method: l, analysis efficiency is low; 2, analyze asynchronous; 3, equipment funds drop into larger.
Object of the present invention is achieved through the following technical solutions: the catalyst test apparatus of CO gaseous oxidation preparing oxalate coupling reaction disclosed by the invention comprises gas control piping system (1), fixed bed reaction system (2), utilidor (3), multiport valve system (4), binary channels gas chromatography system (5) and product tourie (6); Wherein, gas control piping system (1) comprises three road gas control pipelines, each road includes the gas pipe line, pressure maintaining valve (7), tensimeter (11), flow stabilizing valve (8), mass flow controller (9) and the switch valve (10) that connect successively, three road gas control pipelines are merged into a road by straight cross joint, and the pipeline after merging is provided with a general pressure table (11 '); Fixed bed reaction system (2) comprises the quartz tube reactor (12), electric furnace (13) and the temperature controller that are filled with catalyzer (14); Utilidor (3) comprises breather line, heating tape and temperature controller; Multiport valve system (4) comprises pneumatic ten-way valve (15), pneumatic six-way valve (16), quantity tube (17), valve control (18) and insulation can; Binary channels gas chromatography system (5) comprises the first packed column (19), the second packed column (20), capillary column (21), thermal conductivity detector (TCD) (22), flame ionization ditector (23) and computing machine (24);
Wherein, the upper end of quartz tube reactor (12) connects general pressure table (11 '), and lower end connects the entrance of utilidor (3); The outlet of utilidor (3) is connected with pneumatic ten-way valve (15), pneumatic ten-way valve (15) is connected by pipeline with pneumatic six-way valve (16), on pneumatic ten-way valve (15) and pneumatic six-way valve (16), be equipped with quantity tube (17), pneumatic ten-way valve (15) is connected with valve control (18) with pneumatic six-way valve (16); Pneumatic ten-way valve (15) connects the first packed column (19) and the second packed column (20), and the first packed column (19) is connected with thermal conductivity detector (TCD) (22); Pneumatic six-way valve (16) is connected with capillary column (21), and capillary column (21) is connected with flame ionization ditector (23); The outlet pipe of pneumatic six-way valve (16) is connected with product tourie (6).
Preferably, described San road gas control pipeline comprises CO gas pipeline, nitrites gas pipeline and nitrogen argon gas combination gas gas pipeline.
Preferably, there are three root thorns at described quartz tube reactor (12) middle part, for fixed catalyst.
Preferably, the temperature range of described electric furnace (13): room temperature-600 DEG C, temperature-controlled precision: ± 0.2 DEG C.
Preferably, described the first packed column (19) is any in TDX-0l, 5A molecular sieve or 13X molecular sieve, the second packed column (20) is Porapak Q or Porapak N, and capillary column (21) is any in SE-30, OV-10l or PEG-20M.
Preferably, described oxalate is dimethyl oxalate or diethy-aceto oxalate.
Preferably, described nitrites is methyl nitrite or nitrous ether (ethyl nitrite).
The evaluating catalyst method of CO gaseous oxidation preparing oxalate coupling reaction disclosed by the invention is as follows:
L, measure catalyzer (14), put into quartz tube reactor (12) middle part and beat thorn position, inertia silica sand is all filled at two ends up and down;
2, open the first carrier gas, the second carrier gas and the 3rd carrier gas, open chromatogram, make gas chromatography keep ready state;
3, open switch valve (10), control pressure and the flow of unstripped gas by pressure maintaining valve (7), flow stabilizing valve (8), mass flow controller (9);
4, computing machine (24) is controlled the initial peak area of gas chromatography collection unstripped gas;
5, with temperature controller control electric furnace (13) temperature programme to temperature of reaction;
6, unstripped gas is after catalyzer (14) surface reaction, product and unreacted unstripped gas are full of the quantity tube (17) on pneumatic ten-way valve (15) and pneumatic six-way valve (16) in real time by utilidor (3), and gas is walked dotted line pipeline;
7, computing machine (24) is controlled pneumatic ten-way valve (15) and pneumatic six-way valve (16) rotation by valve control (18), gas is walked solid line pipeline, brings the sample in quantity tube (17) into chromatographic column and carries out full constituent Synchronization Analysis;
8, the organism in Organic Ingredients gas nitrites and product goes out peak by capillary column (21) on flame ionization ditector (23), organic product in quantity tube (17) on pneumatic ten-way valve (15) is fallen by blowback by the second packed column (20), residue inorganic raw material gas CO, inert nitrogen gas argon gas and product NO go out peak by the first packed column (19) on thermal conductivity detector (TCD) (22), and this process is synchronously to complete in a gas chromatography;
9, can accurately calculate the conversion ratio of raw material by the variation of chromatographic peak area before and after reaction, the selectivity of principal product oxalate can be accurately calculated by area normalization method, the space-time yield of product oxalate can be accurately calculated by conversion ratio, selectivity and air speed.
Preferably, described range of reaction temperature: 90-160 DEG C, reaction pressure scope: 0.0l-1MPa.
The invention has the beneficial effects as follows:
The catalyst test apparatus of CO gaseous oxidation preparing oxalate coupling reaction disclosed by the invention and evaluating catalyst method only just can realize raw material and the analysis of product full constituent real-time synchronization by the binary channels gas chromatography of an outfit multiport valve system, analysis efficiency is high, accurately and reliably, and fund input is less for data.
Brief description of the drawings
Figure l is the schematic diagram of the catalyst test apparatus of CO gaseous oxidation preparing oxalate coupling reaction disclosed by the invention, wherein: l is gas control piping system, 2 is fixed bed reaction system, 3 is utilidor, 4 is multiport valve system, 5 is binary channels gas chromatography system, 6 is product tourie, 7 is pressure maintaining valve, 8 is flow stabilizing valve, 9 is mass flow controller, 10 is switch valve, 11 is tensimeter, 11 ' be general pressure table, 12 is quartz tube reactor, 13 is electric furnace, 14 is catalyzer, 15 is pneumatic ten-way valve, 16 is pneumatic six-way valve, 17 is quantity tube, 18 is valve control, 19 is the first packed column, 20 is the second packed column, 2l is capillary column, 22 is thermal conductivity detector (TCD), 23 is flame ionization ditector, 24 is computing machine,
Fig. 2 is the gas chromatography flame ionization ditector analysis of spectra of EXAMPLE l catalyzer;
Fig. 3 is the GC thermal conductivity device analysis of spectra of EXAMPLE l catalyzer.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
EXAMPLE l:
The evaluating apparatus that dimethyl oxalate catalyzer is prepared in CO gaseous oxidation coupling disclosed by the invention comprises gas control piping system (1), fixed bed reaction system (2), utilidor (3), multiport valve system (4), binary channels gas chromatography system (5) and product tourie (6); Wherein gas control piping system (1) comprises three road gas control pipelines, and each road includes the gas pipe line, pressure maintaining valve (7), tensimeter (11), flow stabilizing valve (8), mass flow controller (9) and the switch valve (10) that connect successively; Three road gas control pipelines are merged into a road by straight cross joint, and the pipeline after merging is provided with a general pressure table (11 '); Fixed bed reaction system (2) comprises the quartz tube reactor (12), electric furnace (13) and the temperature controller that are filled with catalyzer (14); Utilidor (3) comprises breather line, heating tape and temperature controller; Multiport valve system (4) comprises pneumatic ten-way valve (15), pneumatic six-way valve (16), quantity tube (17), valve control (18) and insulation can; Binary channels gas chromatography system (5) comprises the first packed column (19), the second packed column (20), capillary column (21), thermal conductivity detector (TCD) (22), flame ionization ditector (23) and computing machine (24);
Wherein, the upper end of quartz tube reactor (12) connects general pressure table (11 '), and lower end connects the entrance of utilidor (3); The outlet of utilidor (3) is connected with pneumatic ten-way valve (15), pneumatic ten-way valve (15) is connected by pipeline with pneumatic six-way valve (16), on pneumatic ten-way valve (15) and pneumatic six-way valve (16), be equipped with quantity tube (17), pneumatic ten-way valve (15) is connected with valve control (18) with pneumatic six-way valve (16); Pneumatic ten-way valve (15) connects the first packed column (19) and the second packed column (20), and the first packed column (19) is connected with thermal conductivity detector (TCD) (22); Pneumatic six-way valve (16) is connected with capillary column (21), and capillary column (21) is connected with flame ionization ditector (23); The outlet pipe of pneumatic six-way valve (16) is connected with product tourie (6).
Preferably, described San road gas control pipeline comprises CO gas pipeline, methyl nitrite gas pipeline and nitrogen argon gas combination gas gas pipeline.
Preferably, there are three root thorns at described quartz tube reactor (12) middle part, for fixed catalyst.
Preferably, the temperature range of described electric furnace (13): room temperature-600 DEG C, temperature-controlled precision: ± 0.2 DEG C.
Preferably, described the first packed column (19) is 5A molecular sieve, and the second packed column (20) is Porapak N, and capillary column (21) is SE-30.
Evaluating catalyst method disclosed by the invention is as follows:
L, measure lmL0.5%Pd/ α-Al
2o
3catalyzer (14), puts into quartz tube reactor (12) middle part and beats thorn position, and inertia silica sand is all filled at upper and lower two ends;
2, open the first carrier gas, the second carrier gas and the 3rd carrier gas, open chromatogram, make gas chromatography keep ready state;
3, open switch valve (10), the pressure of controlling unstripped gas by pressure maintaining valve (7), flow stabilizing valve (8), mass flow controller (9) is that 0.1MPa, total flow are 50mL/min;
4, computing machine (24) is controlled the initial peak area of gas chromatography collection unstripped gas;
5, be warming up to 130 DEG C of temperature of reaction with temperature controller control electric furnace (13) with the speed program of 10 DEG C/min;
6, after unstripped gas reacts with catalyzer (14) Surface Contact, product and unreacted unstripped gas are full of the quantity tube (17) on pneumatic ten-way valve (15) and pneumatic six-way valve (16) in real time by utilidor (3), and gas is walked dotted line pipeline;
7, computing machine (24) is controlled pneumatic ten-way valve (15) and pneumatic six-way valve (16) rotation by valve control (18), gas is walked solid line pipeline, brings the sample in quantity tube (17) into chromatographic column and carries out full constituent Synchronization Analysis;
8, the organism in Organic Ingredients gas methyl nitrite and product goes out peak by capillary column (21) on flame ionization ditector (23), organic product in quantity tube (17) on pneumatic ten-way valve (15) is fallen by blowback by the second packed column (20), residue inorganic raw material gas CO, inert nitrogen gas argon gas and product NO go out peak by the first packed column (19) on thermal conductivity detector (TCD) (22), and this process is synchronously to complete in a gas chromatography;
The conversion ratio that 9, can accurately calculate CO by the variation of chromatographic peak area before and after reaction is 69%, can accurately calculate the selectivity 96% of principal product dimethyl oxalate by area normalization method, by CO conversion ratio, dimethyl oxalate selectivity and air speed (3000h
-1) space-time yield that can accurately calculate product dimethyl oxalate is 1479gL
-1h
-1.
Above-described embodiment is only for illustrating composition, connected mode and the evaluating catalyst method of catalyst test apparatus disclosed by the invention; do not limit the present invention; being equal to of all any amendments of doing within the spirit and principles in the present invention, parts replaced and improvement etc., within being all included in protection scope of the present invention.
Claims (9)
1. a catalyst test apparatus for CO gaseous oxidation preparing oxalate coupling reaction, is characterized in that: this evaluating apparatus comprises gas control piping system (1), fixed bed reaction system (2), utilidor (3), multiport valve system (4), binary channels gas chromatography system (5) and product tourie (6);
Wherein:
Gas control piping system (1) comprises three road gas control pipelines, each road includes the gas pipe line, pressure maintaining valve (7), tensimeter (11), flow stabilizing valve (8), mass flow controller (9) and the switch valve (10) that connect successively, three road gas control pipelines are merged into a road by straight cross joint, and the pipeline after merging is provided with a general pressure table (11 ');
Fixed bed reaction system (2) comprises the quartz tube reactor (12), electric furnace (13) and the temperature controller that are filled with catalyzer (14);
Utilidor (3) comprises breather line, heating tape and temperature controller;
Multiport valve system (4) comprises pneumatic ten-way valve (15), pneumatic six-way valve (16), quantity tube (17), valve control (18) and insulation can;
Binary channels gas chromatography system (5) comprises the first packed column (19), the second packed column (20), capillary column (21), thermal conductivity detector (TCD) (22), flame ionization ditector (23) and computing machine (24); Wherein:
The upper end of quartz tube reactor (12) connects general pressure table (11 '), and lower end connects the entrance of utilidor (3);
The outlet of utilidor (3) is connected with pneumatic ten-way valve (15), pneumatic ten-way valve (15) is connected by pipeline with pneumatic six-way valve (16), on pneumatic ten-way valve (15) and pneumatic six-way valve (16), be equipped with quantity tube (17), pneumatic ten-way valve (15) is connected with valve control (18) with pneumatic six-way valve (16);
Pneumatic ten-way valve (15) connects the first packed column (19) and the second packed column (20), and the first packed column (19) is connected with thermal conductivity detector (TCD) (22);
Pneumatic six-way valve (16) is connected with capillary column (21), and capillary column (21) is connected with flame ionization ditector (23); The outlet pipe of pneumatic six-way valve (16) is connected with product tourie (6).
2. according to the catalyst test apparatus described in claim l, it is characterized in that: preferred, gas control pipeline in described San road comprises CO gas pipeline, nitrites gas pipeline and nitrogen argon gas combination gas gas pipeline.
3. according to the catalyst test apparatus described in claim l, it is characterized in that: there are three root thorns at described quartz tube reactor (12) middle part, for fixed catalyst.
4. according to the catalyst test apparatus described in claim l, it is characterized in that: the temperature range of described electric furnace (13): room temperature-600 DEG C, temperature-controlled precision: ± 0.2 DEG C.
5. according to the catalyst test apparatus described in claim l, it is characterized in that: described the first packed column (19) is any in TDX-0l, 5A molecular sieve or 13X molecular sieve, the second packed column (20) is Porapak Q or Porapak N, and capillary column (21) is any in SE-30, OV-10l or PEG-20M.
6. according to the catalyst test apparatus described in claim l, it is characterized in that: oxalate is dimethyl oxalate or diethy-aceto oxalate.
7. catalyst test apparatus according to claim 2, is characterized in that: nitrites is methyl nitrite or nitrous ether (ethyl nitrite).
8. the method for the catalyst test apparatus evaluate catalysts described in right to use requirement l, is characterized in that, evaluation method is as follows:
1) measure catalyzer (14), put into quartz tube reactor (12) middle part and beat thorn position, inertia silica sand is all filled at upper and lower two ends;
2) open the first carrier gas, the second carrier gas and the 3rd carrier gas, open chromatogram, make gas chromatography keep ready state;
3) open switch valve (10), control pressure and the flow of unstripped gas by pressure maintaining valve (7), flow stabilizing valve (8), mass flow controller (9);
4) computing machine (24) is controlled the initial peak area of gas chromatography collection unstripped gas;
5) with temperature controller control electric furnace (13) temperature programme to temperature of reaction;
6) unstripped gas is after catalyzer (14) surface reaction, and product and unreacted unstripped gas are full of the quantity tube (17) on pneumatic ten-way valve (15) and pneumatic six-way valve (16) in real time by utilidor (3);
7) computing machine (24) is controlled pneumatic ten-way valve (15) and pneumatic six-way valve (16) rotation by valve control (18), brings the sample in quantity tube (17) into chromatographic column and carries out full constituent Synchronization Analysis;
8) organism in Organic Ingredients gas nitrites and product goes out peak by capillary column (21) on flame ionization ditector (23), organic product in quantity tube (17) on pneumatic ten-way valve (15) is fallen by blowback by the second packed column (20), residue inorganic raw material gas CO, inert nitrogen gas argon gas and product NO go out peak by the first packed column (19) on thermal conductivity detector (TCD) (22), and this process is synchronously to complete in a gas chromatography;
9) can accurately calculate the conversion ratio of raw material by the variation of chromatographic peak area before and after reaction, the selectivity of principal product oxalate can be accurately calculated by area normalization method, the space-time yield of product oxalate can be accurately calculated by conversion ratio, selectivity and air speed.
9. method according to claim 8, is characterized in that: range of reaction temperature: 90-160 DEG C, reaction pressure scope: 0.0l-lMPa.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110044663A (en) * | 2019-04-18 | 2019-07-23 | 武汉理工大学 | Laboratory flames intermediate product sampling system and analysis method |
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| CN110044663B (en) * | 2019-04-18 | 2020-08-25 | 武汉理工大学 | Laboratory flame intermediate product sampling system and analysis method |
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