CN109745925B - Method for filling direct hydration reactor of n-butene - Google Patents
Method for filling direct hydration reactor of n-butene Download PDFInfo
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- CN109745925B CN109745925B CN201910142478.0A CN201910142478A CN109745925B CN 109745925 B CN109745925 B CN 109745925B CN 201910142478 A CN201910142478 A CN 201910142478A CN 109745925 B CN109745925 B CN 109745925B
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- 238000000034 method Methods 0.000 title claims abstract description 40
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000006703 hydration reaction Methods 0.000 title claims description 18
- 230000036571 hydration Effects 0.000 title claims description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 167
- 238000010926 purge Methods 0.000 claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 238000011010 flushing procedure Methods 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000012535 impurity Substances 0.000 abstract description 29
- 239000000428 dust Substances 0.000 abstract description 26
- 239000010419 fine particle Substances 0.000 abstract description 26
- 230000000887 hydrating effect Effects 0.000 abstract description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 14
- 238000005406 washing Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000005429 filling process Methods 0.000 description 5
- 238000012856 packing Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011027 product recovery Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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Abstract
The invention provides a filling method of a reactor for directly hydrating n-butene, which comprises the following steps: opening a plurality of filling ports on the reactor and a purge valve at the bottom of the reactor; respectively filling catalysts into the plurality of filling openings from top to bottom so as to respectively fill the catalysts into the catalyst bed layers corresponding to the filling openings; closing the plurality of filling ports and the purge valve; filling n-butene material into the reactor, and starting the reactor to work. The technical scheme of the invention effectively solves the problems that the filling method in the prior art needs to consume more flushing agent and dust, fine particles and impurities in the catalyst are accumulated along with the flushing agent.
Description
Technical Field
The invention relates to the technical field of using modes of petrochemical equipment, in particular to a filling method of a direct hydration reactor for n-butene.
Background
The direct hydration method of n-butene is the most important method for producing sec-butanol at home and abroad at present. The method mainly uses resin as a catalyst, n-butene generates sec-butyl alcohol through proton catalysis, the reaction is carried out under a three-phase condition, the reaction temperature is 150-170 ℃, the reaction pressure is 5.0-7.0 MPa, and the molar ratio of water to n-butene is about 1: 1.
The method has the advantages of simple process flow, easy product recovery and refining, less three wastes, small corrosion to equipment and high sec-butyl alcohol selectivity. In actual operation, the n-butene direct hydration reactor is easy to have high pressure drop of a catalyst bed layer, and the catalyst is crushed and leaked, so that a process circulating water system carries the catalyst, the feeding load of the reactor is reduced, the yield of sec-butyl alcohol is reduced, and when the total pressure drop of the reactor exceeds a designed value, the severe consequence of stopping the reactor can be caused.
The hydration reactor comprises a reactor main body and a plurality of catalyst beds, the catalyst beds are transversely arranged and are vertically arranged at intervals, the traditional filling method is that catalyst is filled into the catalyst beds from bottom to top, the catalyst bed at the bottommost layer is filled firstly, a purge valve at the bottom of the reactor is kept normally open during the filling process, and when the catalyst is continuously added to the catalyst filling amount of one bed according to the design requirement, the purge valve at the bottom is closed and a filling port corresponding to the catalyst bed is sealed. And finally, sequentially filling the catalyst bed layers in the reactor with the catalyst to a specified filling amount from bottom to top in the same manner. The washing agent is needed to carry out auxiliary washing in the filling process of the catalyst, and particularly, the washing agent is needed to wash the catalyst bed layer before and after the catalyst is added, so that more washing agent is consumed.
However, the traditional filling method needs to consume more flushing agent, and when the upper catalyst bed layer is filled, dust, fine particles and impurities in the resin catalyst enter the lower catalyst bed layer along with the flushing agent, are accumulated in the catalyst in the lower catalyst bed layer, and are difficult to discharge. Thus, the risk of bed pressure drop increase during the operation of the reactor is increased, and hidden danger is brought to the safe and efficient operation of the reactor.
Disclosure of Invention
The invention mainly aims to provide a filling method of a direct hydration reactor for n-butene, which aims to solve the problems that a large amount of flushing agent needs to be consumed in the filling method in the prior art, and dust, fine particles and impurities in a catalyst are accumulated along with the flushing agent.
In order to achieve the above object, the present invention provides a method for filling a reactor for directly hydrating n-butene, the filling method comprising the steps of: opening a plurality of filling ports on the reactor and a purge valve at the bottom of the reactor; respectively filling catalysts into the plurality of filling openings from top to bottom so as to respectively fill the catalysts into the catalyst bed layers corresponding to the filling openings; closing the plurality of filling ports and the purge valve; filling n-butene material into the reactor, and starting the reactor to work.
Furthermore, when the catalyst bed layer is filled with the catalyst, the flushing agent is added into the catalyst bed layer at the same time, so that the catalyst is uniformly distributed on the catalyst bed layer.
Further, an independent filling opening is arranged above each catalyst bed layer.
Furthermore, a purge pipeline is arranged at the bottom of the reactor, a purge valve is arranged on the purge pipeline, and when the catalyst bed is filled with the catalyst and the flushing agent is added, the purge valve is kept normally open until the catalyst reaches a rated amount.
Further, the purge valve is closed after the catalyst reaches a rated amount.
Further, all fill ports remain open until the purge valve is closed.
Further, after all catalyst on the catalyst bed is filled to a rated amount, all filling ports are closed.
Further, the number of catalyst beds is four, including: a first filling port is arranged above the first catalyst bed layer; a second filling port is arranged above the second catalyst bed layer; a third filling port is arranged above the third catalyst bed layer; a fourth filling port is arranged above the fourth catalyst bed layer; wherein, the first catalyst bed layer, the second catalyst bed layer, the third catalyst bed layer and the fourth catalyst bed layer are arranged in sequence from top to bottom.
Further, the flushing agent is desalted water.
Further, the catalyst is a resin type catalyst.
By applying the technical scheme of the invention, the method for filling the catalyst from top to bottom can effectively reduce dust, fine particles and impurities in the catalyst, when each catalyst bed layer is filled, the lower space is empty, no catalyst exists, the dust, the fine particles and the impurities in the catalyst are easy to drop downwards along with the filling process of the catalyst, and finally, a great amount of dust, fine particles and impurities can drop to the bottom of the reactor and leave the reactor through the purge valve. Therefore, a large amount of dust, fine particles and impurities can be prevented from being accumulated in the catalyst of the lower catalyst bed layer, the risk of rising bed layer pressure during the operation of the reactor is reduced from the source, and the reactor can be operated continuously and at high load. Therefore, the packing mode can effectively avoid the accumulation of dust, fine particles and impurities in the catalyst in the reactor catalyst, so that the hydration reactor can continuously and efficiently operate. The technical scheme of the invention effectively solves the problems that the filling method in the prior art needs to consume more flushing agent and dust, fine particles and impurities in the catalyst are accumulated along with the flushing agent.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows a schematic structural view of an embodiment of the reactor according to the invention.
Wherein the figures include the following reference numerals:
10. a reactor; 11. a reactor body; 12. a first catalyst bed; 121. a first fill port; 13. a second catalyst bed; 131. a second fill port; 14. a third catalyst bed layer; 141. a third fill port; 15. a fourth catalyst bed; 151. a fourth fill port; 16. discharging the pipeline; 161. a purge valve; 17. a n-butene feed inlet; 18. and a distillation outlet.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
Spatially relative terms, such as "above … …," "above … …," "above … …," "above," and the like, may be used herein for ease of description to describe one device or feature's spatial relationship to another device or feature as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if a device in the figures is turned over, devices described as "above" or "on" other devices or configurations would then be oriented "below" or "under" the other devices or configurations. Thus, the exemplary term "above … …" can include both an orientation of "above … …" and "below … …". The device may be otherwise variously oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.
Exemplary embodiments according to the present application will now be described in more detail with reference to the accompanying drawings. These exemplary embodiments may, however, be embodied in many different forms and should not be construed as limited to only the embodiments set forth herein. It is to be understood that these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the exemplary embodiments to those skilled in the art, in the drawings, the thicknesses of layers and regions are exaggerated for clarity, and the same devices are denoted by the same reference numerals, and thus the description thereof will be omitted.
A method of charging a reactor 10 for the direct hydration of n-butenes, the steps of charging comprising:
first, the plurality of filling ports of the reactor 10 and the purge valve 161 at the bottom of the reactor 10 are opened;
secondly, respectively filling catalysts into the plurality of filling ports from top to bottom so as to respectively fill the catalysts into the catalyst bed layers corresponding to the filling ports;
third, the multiple fill ports and purge valve 161 are closed;
finally, the reactor 10 is filled with n-butene material and the reactor 10 begins to operate.
By applying the technical scheme of the embodiment, the method for filling the catalyst from top to bottom can effectively reduce dust, fine particles and impurities in the catalyst, when each catalyst bed layer is filled, the lower space is empty, no catalyst exists, the dust, fine particles and impurities in the catalyst are easy to drop downwards along with the filling process of the catalyst, and finally, a great amount of dust, fine particles and impurities can drop to the bottom of the reactor 10 and leave the reactor 10 through the purge valve 161. Thus, a large amount of dust, fine particles and impurities can be prevented from accumulating in the catalyst of the lower catalyst bed, so that the risk of bed pressure drop increase during the operation of the reactor 10 is reduced from the source, and the reactor 10 can continuously operate at high load. Therefore, the packing manner can effectively prevent dust, fine particles and impurities in the catalyst from accumulating in the catalyst in the reactor 10, so that the hydration reactor 10 can continuously and efficiently operate. The technical scheme of the embodiment effectively solves the problems that the filling method in the prior art needs to consume more flushing agent and dust, fine particles and impurities in the catalyst are accumulated along with the flushing agent.
It is to be noted that the reactor 10 in this embodiment includes a reactor main body 11 and a plurality of catalyst beds provided inside the reactor main body.
As shown in fig. 1, in the solution of this embodiment, when the catalyst bed is filled with catalyst, a flushing agent is added to the catalyst bed at the same time, so that the catalyst is uniformly distributed on the catalyst bed. The flushing agent in the above steps can further make dust, fine particles and impurities in the catalyst easily flow with the flushing agent and be discharged out of the reactor 10 from the purge valve 161 at the bottom of the reactor 10, further avoid the dust, fine particles and impurities in the catalyst from accumulating in the lower catalyst bed layer, thus can further reduce the risk of bed pressure drop increase during the operation of the reactor 10, and make the reactor 10 operate continuously and at high load.
It is noted that the above steps combined with top-down filling can reduce the amount of rinse used, and may not even require the addition of additional water for assistance. The traditional filling mode also needs to add a large amount of water, and the working procedure of adding water is omitted in the embodiment, so that the filling efficiency can be greatly improved; and the top-down filling mode can avoid the residual impurities after the washing of the upper catalyst bed layer from entering the lower catalyst bed layer, so that the catalyst needing to be washed is only washed once, the waste of the washing agent in the traditional washing for many times is avoided, and the consumption of the washing agent can be reduced.
In the solution of this embodiment, as shown in fig. 1, a separate filling port is provided above each catalyst bed. The structure can ensure that each catalyst bed layer is mutually independent and not interfered with each other.
As shown in fig. 1, in the solution of this embodiment, a purge line 16 is disposed at the bottom of the reactor 10, a purge valve 161 is disposed on the purge line 16, and when the catalyst bed is filled with catalyst and a flushing agent is added, the purge valve 161 is kept normally open until the catalyst reaches a rated amount. The purge line 16 and purge valve 161 are provided to better drain excess liquid and impurities from the reactor 10. The purge valve 161 is normally open to ensure that dust, fine particles, impurities, etc. flushed from the flushing agent can be discharged in time, thereby preventing the purge pipe 16 from being blocked.
As shown in fig. 1, in the solution of the present embodiment, after the catalyst reaches the rated amount, the purge valve 161 is closed. The above steps can prevent n-butene from leaking out of the position of the purge valve 161. It is noted that the purge valve 161 is preferably closed after the catalyst has reached a nominal amount and dust, fine particles, impurities, etc. have been removed.
In the solution of the present embodiment, as shown in fig. 1, all filling ports are kept open before the purge valve 161 is closed. This prevents the reactor 10 from being negatively pressurized and failing to discharge dust, fine particles, impurities, etc.
As shown in fig. 1, in the solution of this example, all the filling ports are closed after all the catalyst on the catalyst bed is filled to the rated amount. The above steps are provided for the operation of the reactor 10, so as to prevent n-butene from leaking from the position of the charging port and prevent external impurities from entering the reactor 10.
As shown in fig. 1, in the technical solution of this embodiment, the number of the catalyst beds is four, and the catalyst beds include a first catalyst bed 12, a second catalyst bed 13, a third catalyst bed 14, and a fourth catalyst bed 15. A first filling opening 121 is arranged above the first catalyst bed layer 12; a second filling opening 131 is arranged above the second catalyst bed layer 13; a third filling port 141 is arranged above the third catalyst bed layer 14; a fourth filling opening 151 is arranged above the fourth catalyst bed layer 15; wherein, the first catalyst bed layer 12, the second catalyst bed layer 13, the third catalyst bed layer 14 and the fourth catalyst bed layer 15 are arranged in sequence from top to bottom. The structure is a preferable structure, and other layers of catalyst beds can be arranged according to actual requirements.
As shown in fig. 1, in the technical solution of this embodiment, the flushing agent is desalted water. This allows better washing of the catalyst while avoiding reaction with the catalyst.
As shown in fig. 1, in the embodiment of the present invention, the catalyst is a resin type catalyst. The catalyst can better perform direct hydration reaction of n-butene. The resin-type catalyst is preferably a strongly acidic cation exchange resin having good heat resistance. Fresh resin-type catalysts are preferred.
It is noted that the method of the present invention uses resin as a catalyst, so that n-butene generates sec-butyl alcohol through proton catalysis, and the reaction is carried out under a three-phase condition. The reaction temperature is 150-170 ℃, and the reaction pressure is 5.0-7.0 MPa. The molar ratio of water to n-butene was about 1: 1. The method has the advantages of simple process flow, easy product recovery and refining, less three wastes, small corrosion to equipment and high sec-butyl alcohol selectivity. The water is desalted water to avoid the influence of salt components on the direct hydration reaction of n-butylene. The present invention has a n-butene feed inlet 17 and is preferably located at the bottom of the reactor 10, and the top of the reactor 10 is provided with a distillation outlet 18 to distill off and store the sec-butanol produced.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: by applying the technical scheme of the invention, the method for filling the catalyst from top to bottom can effectively reduce dust, fine particles and impurities in the catalyst, when each catalyst bed layer is filled, the lower space is empty, no catalyst exists, the dust, fine particles and impurities in the catalyst are easy to fall down along with the filling process of the catalyst, and finally, a great amount of dust, fine particles and impurities can fall to the bottom of the reactor 10 and leave the reactor 10 through the purge valve 161. Thus, a large amount of dust, fine particles and impurities can be prevented from accumulating in the catalyst of the lower catalyst bed, so that the risk of bed pressure drop increase during the operation of the reactor 10 is reduced from the source, and the reactor 10 can continuously operate at high load. Therefore, the packing manner can effectively prevent dust, fine particles and impurities in the catalyst from accumulating in the catalyst in the reactor 10, so that the hydration reactor 10 can continuously and efficiently operate. The technical scheme of the invention effectively solves the problems that the filling method in the prior art needs to consume more flushing agent and dust, fine particles and impurities in the catalyst are accumulated along with the flushing agent.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
It should be noted that the terms "first," "second," and the like in the description and claims of this application and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A method for charging a reactor for the direct hydration of n-butenes, comprising the steps of:
opening a plurality of filling ports on a reactor (10) and a purge valve (161) at the bottom of the reactor (10);
respectively filling catalysts into the plurality of filling ports from top to bottom so as to respectively fill the catalysts into the catalyst beds corresponding to the filling ports;
closing the plurality of fill ports and the purge valve (161);
filling n-butene materials into the reactor (10), and starting the reactor (10) to work;
when the catalyst bed layer is filled with the catalyst, simultaneously adding a flushing agent into the catalyst bed layer so as to ensure that the catalyst is uniformly distributed on the catalyst bed layer.
2. The method of claim 1, wherein a separate filling port is provided above each catalyst bed.
3. The method for filling a n-butene direct hydration reactor according to claim 2 wherein a purge line (16) is provided at the bottom of the reactor (10), the purge valve (161) is provided on the purge line (16), and the purge valve (161) is kept normally open to a nominal amount of catalyst when the catalyst bed is filled with the catalyst and the flushing agent is added.
4. The method of claim 3, wherein the purge valve (161) is closed after the catalyst reaches a rated amount.
5. The method of claim 4, wherein all the fill ports are kept open before the purge valve (161) is closed.
6. The method of claim 5, wherein all of the filling ports are closed after all of the catalyst on the catalyst bed is filled to a rated amount.
7. The method of filling a n-butene direct hydration reactor of claim 1 wherein the number of catalyst beds is four, comprising:
a first catalyst bed layer (12), wherein a first filling opening (121) is arranged above the first catalyst bed layer (12);
a second catalyst bed layer (13), wherein a second filling opening (131) is arranged above the second catalyst bed layer (13);
a third catalyst bed layer (14), wherein a third filling opening (141) is arranged above the third catalyst bed layer (14);
a fourth catalyst bed layer (15), wherein a fourth filling opening (151) is arranged above the fourth catalyst bed layer (15);
wherein the first catalyst bed layer (12), the second catalyst bed layer (13), the third catalyst bed layer (14) and the fourth catalyst bed layer (15) are sequentially arranged from top to bottom.
8. The method of charging a n-butene direct hydration reactor of claim 1 wherein the flushing agent is desalted water.
9. The method of charging a n-butene direct hydration reactor of claim 1 wherein the catalyst is a resin type catalyst.
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| DE10050627A1 (en) * | 2000-10-12 | 2002-04-18 | Bayer Ag | Process for the preparation of tertiary alcohols by hydration of tertiary olefins in a reactive rectification using a structured multipurpose package |
| DE102007006647A1 (en) * | 2007-02-06 | 2008-08-07 | Basf Se | Process for the regeneration of a catalyst bed deactivated in the context of a heterogeneously catalyzed partial dehydrogenation of a hydrocarbon |
| US8206654B2 (en) * | 2008-01-07 | 2012-06-26 | Univation Technologies, Llc | Catalyst feed systems and methods for using the same |
| CN101560413A (en) * | 2009-05-15 | 2009-10-21 | 中国科学院广州能源研究所 | Method for automatic thermocatalytic reforming and purification of biomass fuel gas and device |
| CN101804314A (en) * | 2010-05-12 | 2010-08-18 | 新奥新能(北京)科技有限公司 | Fluidized bed reactor |
| CN102876373B (en) * | 2011-07-11 | 2015-04-01 | 中国石油化工股份有限公司 | Method for prolonging running period of hydrotreatment device |
| CN102814150B (en) * | 2012-09-04 | 2014-08-20 | 山东齐鲁石化工程有限公司 | Radial fixed bed oxidative dehydrogenation reactor for regenerating catalyst by sections |
| CN203540502U (en) * | 2013-10-23 | 2014-04-16 | 中国石油化工股份有限公司 | Novel hydration reactor |
| CN104353255B (en) * | 2014-11-07 | 2017-09-19 | 安徽泰合森能源科技有限责任公司 | A kind of filling device of catalytic distillation catalyst |
| CN105413593B (en) * | 2015-12-24 | 2018-06-22 | 李劲 | Duct type gas-solid phase reactor |
| CN205462142U (en) * | 2016-01-08 | 2016-08-17 | 东华工程科技股份有限公司 | Direct synthetic reactor structure of gathering methoxy methylal of one -step method |
| CN105693479A (en) * | 2016-03-15 | 2016-06-22 | 江苏凯茂石化科技有限公司 | Process device special for preparing polyoxymethylene dimethyl ethers through formaldehyde gas |
| CN206454654U (en) * | 2017-01-25 | 2017-09-01 | 天津大学 | The packed catalytic rectification packing of disc type assembling |
| CN107511115A (en) * | 2017-08-31 | 2017-12-26 | 天津市鹏翔科技有限公司 | A kind of packing method of fine catalyst |
| CN108816294B (en) * | 2018-06-21 | 2021-04-02 | 浦江思欣通科技有限公司 | Fixed bed Fischer-Tropsch iron catalyst activation pretreatment method |
| CN109107495B (en) * | 2018-08-31 | 2021-04-20 | 中国海洋大学 | Method for directly loading and filling photocatalyst in layered mode and component thereof |
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