CN100497284C - Reaction system for preparation of formaldehyde and ethylene by sectionally catalyzing natural gas with heteropoly acid/molecular sieve - Google Patents
Reaction system for preparation of formaldehyde and ethylene by sectionally catalyzing natural gas with heteropoly acid/molecular sieve Download PDFInfo
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- CN100497284C CN100497284C CNB2007100721363A CN200710072136A CN100497284C CN 100497284 C CN100497284 C CN 100497284C CN B2007100721363 A CNB2007100721363 A CN B2007100721363A CN 200710072136 A CN200710072136 A CN 200710072136A CN 100497284 C CN100497284 C CN 100497284C
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Abstract
The invention relates to a method and a reacting system for preparing the formaldehyde and ethene which catalyzes natural gas by the heteropoly acid and the molecular screen. The invention solves the problems such as low yield of formaldehyde and ethene by natural gas and industrialisation difficulty. The invention comprises following steps: a. mixing the natural gas and compressed air; b. adding water into the complex gas, and vaporizing; c. a length of catalytic reaction; condensating; f. separating. The gas outlet of the first gas inlet of the first flowmeter of the first gas inlet valve of the reacting system connects to the gas inlet of the mixing machine of the first thermometric with a first air pressure measure. The second gas inlet having the second gas inlet valve and second flowmeter connects to the gas inlet of the mixing machine of the first thermometric with a first air pressure measure. The inventive methane percent conversion is 29.8%. The method and apparatus of the invention is suitable for industrialisation. The reacting system of the invention is simple and easy to operate.
Description
Technical field
The present invention relates to the reaction unit that a kind of Sweet natural gas prepares formaldehyde and ethene.
Background technology
Ethylene yield is one of important symbol of a national petrochemical complex and the level of economic development, and the Sweet natural gas technique for producing ethylene of non-petroleum path is one of main route of utilizing of gas chemical industry.At present, the Sweet natural gas technological line of producing alkene mainly contains following several:
(1) methane oxidation coupling route is produced alkene by methane one step;
(2) chlorination route is a monochloro methane with methane conversion at first, takes off HCl again and is converted into ethene;
(3) synthetic gas route is a synthetic gas with methane conversion at first, again through Fischer-Tropsch reaction synthesizing ethylene;
(4) ethanol route is a synthetic gas with methane conversion earlier, again through the synthetic ethanol that generates of catalysis, dewater again and ethene;
(5) dme route is a synthetic gas with methane conversion, again by synthesizing dimethyl ether by synthetic gas dehydration system ethene;
(6) methyl alcohol route, by synthesising gas systeming carbinol, cracking generates ethene then.
Progress to above six kinds of operational paths differs, and does not but also realize industrialization fully, and at present most economical is the methane oxidation coupling operational path with being hopeful to realize industrialized.Recent two decades comes, and this technology is subjected to various countries and payes attention to, the UCC of the U.S. (Union Carbide Corp, Arco company), and Australian Union's science and industrial organization, countries such as member country of the Commonwealth of Independent States and Iran are are all researching and developing.Domestic have tens tame units in the R﹠D work of carrying out this project, be put into " eight or five " state key brainstorm project as most important problem in the Sweet natural gas comprehensive utilization, the carrier mainly contains Dalian Chemiclophysics Inst., Chinese Academy of Sciences, Lanzhou chemical physics institute and Chengdu organic chemistry institute.In recent years in this reaction mechanism, new catalyst, aspects such as reaction process and reactor have obtained certain progress.But because this reaction kinetic control of originally experiencing, methane conversion is lower than 25%, and the influence of the UCC company of the U.S. is failed to break away from the research aspect of catalyzer, so to reach methane conversion be that 30% industrialized level still has a segment distance.
In recent years, because the deposit atrophy of petroleum resources, the status of Sweet natural gas in industrial chemicals becomes increasingly conspicuous.To make energy structure and chemical industry resource structures generation major transformation.For this tachnical storage of doing is the research topic that people very pay close attention to.Under the soaring situation of oil price, utilize oxidative coupling of methane stage by stage effectively with methyl hydride catalyzed formaldehyde and the ethene that is converted into high added value of the main component of Sweet natural gas, minimizing has important techniques and economic attractiveness to the undue dependence of petroleum resources.
Summary of the invention
To the objective of the invention is that present Sweet natural gas prepares formaldehyde and ethylene yield is low in order solving, can not to realize industrialized problem, provide a kind of heteropolyacid/molecular sieve segmentation catalyzing natural gas to prepare the reactive system of formaldehyde and ethene.The step that Sweet natural gas of the present invention prepares formaldehyde and ethene method is as follows: a, Sweet natural gas being mixed with pressurized air, is 1～2:1 with methane and compressed-air actuated volume ratio in the under meter control Sweet natural gas, and two kinds of unstripped gas total fluxs are 40～80ml/min; B, add water in gas mixture, discharge is 5～10mL/min, vaporizes under 120～150 ℃ of conditions; C, one section catalyzed reaction: under 200～300 ℃, 1.1～1.3atm condition, the molecular sieve catalytic gas mixture with carried heteropoly acid catalyst is converted into formaldehyde with gas mixture, and the load ratio of heteropolyacid catalyst is 5～15%; D, two sections catalyzed reactions: under 780～820 ℃ of conditions, the gas mixture of molecular sieve catalytic after step c handles with carried heteropoly acid catalyst is converted into ethene with gas mixture, and heteropolyacid catalyst load ratio is 5～15%; E, the product condensation after steps d handled; F, product is separated with separator, promptly obtain formaldehyde and ethene.
Sweet natural gas of the present invention prepares formaldehyde and ethylene reaction system and is made up of first inlet pipe, second inlet pipe, mixing tank, emptying tracheae, first pipe connecting, vaporizer, second pipe connecting, first fixed-bed reactor, the 3rd pipe connecting, second fixed-bed reactor, the 4th pipe connecting, cold-trap, the 5th pipe connecting, separator, the escape pipe that has air outlet valve, the water inlet pipe that has the drain pipe of liquid-outlet valve and have a volume pump; The air outlet of first inlet pipe is communicated with the inlet mouth of mixing tank, the air outlet of second inlet pipe is communicated with the inlet mouth of mixing tank, mixing tank is communicated with by first pipe connecting with vaporizer, the water outlet that has the water inlet pipe of volume pump is communicated with the water-in of vaporizer, vaporizer is communicated with by second pipe connecting with first fixed-bed reactor, first fixed-bed reactor are communicated with by the 3rd pipe connecting with second fixed-bed reactor, second fixed-bed reactor are communicated with by the 4th pipe connecting with cold-trap, first pipe connecting, second pipe connecting, the 3rd pipe connecting and the 4th pipe connecting are provided with blow-down pipe, cold-trap is communicated with by the 5th pipe connecting with separator, the air outlet of separator is communicated with the inlet mouth of the escape pipe that has air outlet valve, and the liquid outlet of separator is communicated with the fluid inlet of the drain pipe that has liquid-outlet valve.
First fixed-bed reactor and second fixed-bed reactor by raw material inlet pipe, thermopair, flange, reaction tube, catalyst filling layer, reflect tracheae and sleeve and form; The raw material inlet pipe is communicated with by flange with reaction tube, the air outlet of reaction tube is communicated with the inlet mouth that reflects tracheae, the catalyst filling layer is equipped with at middle part in the reaction tube, fixedly connected with the lower flange of flange in the telescopic upper end, the middle part of reaction tube is stretched in the telescopic lower end, thermopair is housed in the sleeve, the inlet mouth of the raw material inlet pipe of first fixed-bed reactor is communicated with the air outlet of second pipe connecting, the air outlet that reflects tracheae of first fixed-bed reactor is communicated with the inlet mouth of the 3rd pipe connecting, the air outlet of the 3rd pipe connecting is communicated with the inlet mouth of the raw material inlet pipe of second fixed-bed reactor, and the tracheae that reflects of second fixed-bed reactor is communicated with the 4th pipe connecting.
The present invention uses colloidal sol-gel technique, and (Fe, Cu) etc. serial heteropolyacid/molecular sieve catalyst loads on the silica supports with synthetic P-Mo-V-Mn.The present invention adopts heteropolyacid/molecular sieve catalyst catalyzed oxidation to produce formaldehyde and ethene Sweet natural gas gradient increased temperature stage by stage, makes the productive rate of formaldehyde reach 6.8%, and ethylene yield reaches 23%, improves methane conversion and reaches 29.8%.Device of the present invention is applicable to suitability for industrialized production.Reactive system technology of the present invention is simple, is convenient to operation.
Description of drawings
Fig. 1 is the one-piece construction synoptic diagram of reactive system of the present invention, and Fig. 2 is the structural representation of fixed-bed reactor; 1 is intake valve among the figure, the 2nd, and under meter, the 3rd, weather gage, the 4th, thermometer.
Embodiment
Embodiment one: the step of method that the present embodiment Sweet natural gas prepares formaldehyde and ethene is as follows: a, Sweet natural gas is mixed with pressurized air, with methane and compressed-air actuated volume ratio in the under meter control Sweet natural gas is 1～2:1, and two kinds of unstripped gas total fluxs are 40～80ml/min; B, add water in gas mixture, discharge is 5～10mL/min, vaporizes under 120～150 ℃ of conditions; C, one section catalyzed reaction: under 200～300 ℃, 1.1～1.3atm condition, the molecular sieve catalytic gas mixture with carried heteropoly acid catalyst is converted into formaldehyde with gas mixture, and the load ratio of heteropolyacid catalyst is 5～15%; D, two sections catalyzed reactions: under 780～820 ℃ of conditions, the gas mixture of molecular sieve catalytic after step c handles with carried heteropoly acid catalyst is converted into ethene with gas mixture, and heteropolyacid catalyst load ratio is 5～15%; E, the product condensation after steps d handled; F, product is separated with separator, promptly obtain formaldehyde and ethene.
Embodiment two: present embodiment in step a in the Sweet natural gas methane and compressed-air actuated volume ratio be 1.2～1.8:1.Other is identical with embodiment one.
Embodiment three: in the present embodiment in the Sweet natural gas methane and compressed-air actuated volume ratio be 1.5: 1.Other is identical with embodiment one.
Embodiment four: present embodiment heteropolyacid catalyst in step c is H
4PMo
11VO
40Other is identical with embodiment one.
Embodiment five: present embodiment temperature of reaction in step c is 220～280 ℃.Other is identical with embodiment one.
Embodiment six: the material of molecular sieve is SiO in the present embodiment
2, the aperture is 1～2nm.
Embodiment seven: present embodiment heteropolyacid catalyst in steps d is Na
2MoO
4-Na
2WO
4-MnO
2Na
2MoO
4, Na
2WO
4With MnO
2Mass ratio be 2.5～5:2～4:1.Other is identical with embodiment one.
Embodiment eight: present embodiment temperature of reaction in steps d is 800 ℃.Other is identical with embodiment one.
Embodiment nine: Sweet natural gas prepares formaldehyde and ethylene reaction system by first inlet pipe 5 in the present embodiment, second inlet pipe 6, mixing tank 7, emptying tracheae 10, first pipe connecting 11, vaporizer 12, second pipe connecting 15, first fixed-bed reactor 16, the 3rd pipe connecting 17, second fixed-bed reactor 18, the 4th pipe connecting 19, cold-trap 20, the 5th pipe connecting 21, separator 22, the escape pipe 23 that has air outlet valve 24, the drain pipe 25 that has liquid-outlet valve 26 is formed with the water inlet pipe 28 that has volume pump 27; The air outlet of first inlet pipe 5 is communicated with the inlet mouth of mixing tank 7, the air outlet of second inlet pipe 6 is communicated with the inlet mouth of mixing tank 7, mixing tank 7 is communicated with by first pipe connecting 11 with vaporizer 12, the water outlet that has the water inlet pipe 28 of volume pump 27 is communicated with the water-in of vaporizer 12, vaporizer 12 is communicated with by second pipe connecting 15 with first fixed-bed reactor 16, first fixed-bed reactor 16 are communicated with by the 3rd pipe connecting 17 with second fixed-bed reactor 18, second fixed-bed reactor 18 are communicated with by the 4th pipe connecting 19 with cold-trap 20, first pipe connecting 11, second pipe connecting 15, the 3rd pipe connecting 17 and the 4th pipe connecting 19 are provided with blow-down pipe 10, cold-trap 20 is communicated with by the 5th pipe connecting 21 with separator 22, the air outlet of separator 22 is communicated with the inlet mouth of the escape pipe 23 that has air outlet valve 24, and the liquid outlet of separator 22 is communicated with the fluid inlet of the drain pipe 25 that has liquid-outlet valve 26.
Embodiment ten: in the present embodiment first fixed-bed reactor 16 and second fixed-bed reactor 18 by raw material inlet pipe 29, thermopair 34, flange 30, reaction tube 31, catalyst filling layer 32, reflect tracheae 33 and sleeve 35 and form; Raw material inlet pipe 29 is communicated with by flange 30 with reaction tube 31, the air outlet of reaction tube 31 is communicated with the inlet mouth that reflects tracheae 33, catalyst filling layer 32 is equipped with at middle part in the reaction tube 31, fixedly connected with the lower flange of flange 30 in the upper end of sleeve 35, the middle part of reaction tube 31 is stretched in the lower end of sleeve 35, thermopair 34 is housed in the sleeve 35, the inlet mouth of the raw material inlet pipe 29 of first fixed-bed reactor 16 is communicated with the air outlet of second pipe connecting 15, the air outlet that reflects tracheae 33 of first fixed-bed reactor 16 is communicated with the inlet mouth of the 3rd pipe connecting 17, the air outlet of the 3rd pipe connecting 17 is communicated with the inlet mouth of the raw material inlet pipe 29 of second fixed-bed reactor 18, and the tracheae 33 that reflects of second fixed-bed reactor 18 is communicated with the 4th pipe connecting 19.Other is identical with embodiment nine.
Following evidence effect of the present invention is arranged:
It is raw material that the methane of purity 99% replaces Sweet natural gas, and the reactive system of employing embodiment nine makes ethene and two kinds of products of liquid formaldehyde with the method for embodiment one, analyzes with chromatogram, and test-results is as follows:
1, one section catalyzed reaction methane conversion is a formaldehyde, methane conversion 5～7%; Two sections catalyzed reactions: methane conversion is an ethene, the transformation efficiency 22～25% of ethene.
2, the selectivity of formaldehyde reaches 60～70% in the product, and ethene reaches 45～60%.
3, the output of a flow process, formaldehyde 300 grams per liters hour, ethene reaches 250 gram/cubic meter Sweet natural gases.
4, the productive rate of product: formaldehyde 6.8%, ethene 23% (content of C2 in the hydrocarbon).
Claims (2)
1, heteropolyacid/molecular sieve segmentation catalyzing natural gas prepares the reactive system of formaldehyde and ethene, and this reactive system is by first inlet pipe (5), second inlet pipe (6), mixing tank (7), emptying tracheae (10), first pipe connecting (11), vaporizer (12), second pipe connecting (15), first fixed-bed reactor (16), the 3rd pipe connecting (17), second fixed-bed reactor (18), the 4th pipe connecting (19), cold-trap (20), the 5th pipe connecting (21), separator (22), the escape pipe (23) that has air outlet valve (24), the water inlet pipe (28) that has the drain pipe (25) of liquid-outlet valve (26) and have volume pump (27) is formed; The air outlet that it is characterized in that first inlet pipe (5) is communicated with the inlet mouth of mixing tank (7), the air outlet of second inlet pipe (6) is communicated with the inlet mouth of mixing tank (7), mixing tank 7 is communicated with by first pipe connecting (11) with vaporizer (12), the water outlet that has the water inlet pipe (28) of volume pump (27) is communicated with the water-in of vaporizer (12), vaporizer (12) is communicated with by second pipe connecting (15) with first fixed-bed reactor (16), first fixed-bed reactor (16) are communicated with by the 3rd pipe connecting (17) with second fixed-bed reactor (18), second fixed-bed reactor (18) are communicated with by the 4th pipe connecting (19) with cold-trap (20), first pipe connecting (11), second pipe connecting (15), the 3rd pipe connecting (17) and the 4th pipe connecting (19) are provided with blow-down pipe (10), cold-trap (20) is communicated with by the 5th pipe connecting (21) with separator (22), the air outlet of separator (22) is communicated with the inlet mouth of the escape pipe that has air outlet valve (24) (23), and the liquid outlet of separator (22) is communicated with the fluid inlet of the drain pipe that has liquid-outlet valve (26) (25).
2, heteropolyacid according to claim 1/molecular sieve segmentation catalyzing natural gas prepares the reactive system of formaldehyde and ethene, it is characterized in that first fixed-bed reactor (16) and second fixed-bed reactor (18) by raw material inlet pipe (29), thermopair (34), flange (30), reaction tube (31), catalyst filling layer (32), reflect tracheae (33) and sleeve (35) and form; Raw material inlet pipe (29) is communicated with by flange (30) with reaction tube (31), the air outlet of reaction tube (31) is communicated with the inlet mouth that reflects tracheae (33), catalyst filling layer (32) is equipped with at middle part in the reaction tube (31), fixedly connected with the lower flange of flange (30) in the upper end of sleeve (35), the middle part of reaction tube (31) is stretched in the lower end of sleeve (35), and thermopair (34) is housed in the sleeve (35).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100721363A CN100497284C (en) | 2007-04-29 | 2007-04-29 | Reaction system for preparation of formaldehyde and ethylene by sectionally catalyzing natural gas with heteropoly acid/molecular sieve |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100721363A CN100497284C (en) | 2007-04-29 | 2007-04-29 | Reaction system for preparation of formaldehyde and ethylene by sectionally catalyzing natural gas with heteropoly acid/molecular sieve |
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| Publication Number | Publication Date |
|---|---|
| CN101037383A CN101037383A (en) | 2007-09-19 |
| CN100497284C true CN100497284C (en) | 2009-06-10 |
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| CNB2007100721363A Expired - Fee Related CN100497284C (en) | 2007-04-29 | 2007-04-29 | Reaction system for preparation of formaldehyde and ethylene by sectionally catalyzing natural gas with heteropoly acid/molecular sieve |
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| CN (1) | CN100497284C (en) |
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2007
- 2007-04-29 CN CNB2007100721363A patent/CN100497284C/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| 天然气制低碳烯烃技术及其工艺进展. 李选志.当代化工，第33卷第6期. 2004 |
| 天然气制低碳烯烃技术及其工艺进展. 李选志.当代化工，第33卷第6期. 2004 * |
| 甲烷氧化偶联制乙烯新型催化剂与工艺应用研究. 王海南等.石油与天然气化工，第29卷第6期. 2000 |
| 甲烷氧化偶联制乙烯新型催化剂与工艺应用研究. 王海南等.石油与天然气化工，第29卷第6期. 2000 * |
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