CN111411025A - Hydrogen circulation device for solving contradiction between decarburization and desulfurization and control method thereof - Google Patents
Hydrogen circulation device for solving contradiction between decarburization and desulfurization and control method thereof Download PDFInfo
- Publication number
- CN111411025A CN111411025A CN202010234368.XA CN202010234368A CN111411025A CN 111411025 A CN111411025 A CN 111411025A CN 202010234368 A CN202010234368 A CN 202010234368A CN 111411025 A CN111411025 A CN 111411025A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- recycle hydrogen
- reactor
- mixer
- recycle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a recycle hydrogen device for solving the contradiction between decarburization and desulfurization and a control method thereof, wherein the recycle hydrogen device for solving the contradiction between decarburization and desulfurization comprises a recycle hydrogen liquid separating tank, the recycle hydrogen liquid separating tank is sequentially connected with a purifying tank, a PSA device, a fresh hydrogen compressor, a first mixer, a heat exchanger, a first reactor, a second mixer, a heating device, a second reactor and a third reactor, the recycle hydrogen liquid separating tank is connected with the recycle hydrogen compressor, and the recycle hydrogen compressor is respectively connected with the second mixer and the first mixer through a switch. The first reactor of the invention adopts purified circulating hydrogen and new hydrogen, and does not produce carbonylation reaction with metal nickel in the catalyst, while the second reactor and the third reactor have high reaction temperature, and do not produce carbonylation reaction although the circulating hydrogen contains CO, and in addition, the circulating hydrogen contains H2S can be used as a sulfur source for the on-line vulcanization of a hydrogenation catalyst, thereby decomposingThe contradiction between the CO removal of the recycle hydrogen and the sulfur balance of the catalyst is solved.
Description
Technical Field
The invention belongs to the technical field of circulating hydrogen, and particularly relates to a circulating hydrogen device for solving the contradiction between decarburization and desulfurization and a control method thereof.
Background
At present, the development of the biodiesel industry in China starts late, the esterification or ester exchange technology is adopted all the time, the product is mainly fatty acid methyl ester, the quality is poor, the heat value is low, the acid value is high, the mixing proportion is small, the production cost is high, the product can not be used independently, the mixing proportion is too small, and the product is difficult to accept in the market. The technology for producing the second-generation biodiesel by catalytic hydrodeoxygenation is developed rapidly in recent years, a plurality of devices are put into production in China, and the product quality is greatly improved. However, the waste animal and plant oleic acid has extremely high value and the contents of organic calcium, organic chloride and iron ions are extremely high, so that the catalyst of the reactor is inactivated, a bed layer is scaled, equipment is corroded, and the device is in a state of starting and stopping. In addition, the technical problems of the devices from the catalyst to the reactor to the process flow which basically adopts a refinery diesel oil hydrofining device are not solved.
The prior process of hydrodeoxygenation of waste animal and vegetable oil has the following problems: the hydrogenation deoxidation water and the hydrogenation decarboxylation water to CO2, and the hydrogenation decarbonylation to CO, wherein the three reactions are carried out simultaneously. CO generated by decarbonylation enters the circulating hydrogen and is accumulated continuously, when the CO content in the circulating hydrogen is more than 20ppm and the reaction temperature is lower than 220 ℃ and reaches 180 ℃, the CO and the active component metallic nickel in the hydrogenation catalyst are subjected to carbonylation reaction to generate nickel carbonyl, so that the active component metallic nickel of the hydrogenation catalyst is reduced, the activity of the hydrogenation catalyst is reduced, and therefore the CO in the circulating hydrogen must be removed by adopting a PSA method.
The recycle hydrogen contains not only CO but also H2S, whereas H2S is a poison to the PSA and must be removed before entering the PSA. The removal of H2S from the recycle hydrogen creates a new problem, and the hydrogenation catalyst is only active in the sulfided state. In the process of hydrodeoxygenation, sulfur on the catalyst is replaced by oxygen, generated H2S enters circulating hydrogen, and as long as the content of H2S in the circulating hydrogen is kept to be more than 200ppm, H2S of the circulating hydrogen carries out on-line vulcanization on the catalyst to maintain the activity of the catalyst. The removal of H2S in the recycle hydrogen is forced in order to remove CO in the recycle hydrogen, thereby breaking the sulfur balance of the hydrogenation catalyst and causing the catalyst to be deactivated. In order to maintain the activity of the catalyst, a sulfur supplement agent must be injected into the raw material, the sulfur supplement agent is converted into H2S in the hydrogenation reaction process and is carried into the recycle hydrogen, H2S needs to be removed before the recycle hydrogen enters PSA and enters the whole plant tail gas, so that the tail gas desulfurization load is increased, and therefore, a process flow for solving the contradiction between the recycle hydrogen CO removal and the catalyst sulfur balance is imperative.
Disclosure of Invention
In order to solve the problems, the invention provides a recycle hydrogen device for solving the contradiction between decarburization and desulfurization, which adopts three-stage selective hydrogenation saturation, demetalization and deoxidation process, thereby solving the contradiction between CO removal of recycle hydrogen and sulfur balance of a catalyst.
Another object of the present invention is to provide a method for controlling a hydrogen circulation apparatus which solves the contradiction between decarburization and desulfurization.
The technical scheme adopted by the invention is as follows:
the utility model provides a solve decarbonization and desulfurization contradictory circulating hydrogen device, its includes circulating hydrogen knockout drum, circulating hydrogen knockout drum connects gradually purifying tank, PSA device, new hydrogen compressor, first blender, heat exchanger, first reactor, second blender, heating device, second reactor and third reactor, circulating hydrogen compressor is connected to circulating hydrogen knockout drum, circulating hydrogen compressor connects the second blender respectively and connects first blender through the switch.
Preferably, the reaction temperature in the first reactor is 200-.
Preferably, the reaction temperature in the second reactor is 310-.
Preferably, the reaction temperature in the third reactor is 360-380 ℃.
The other technical scheme of the invention is realized as follows:
a control method of a recycle hydrogen device based on the solution of contradiction between decarburization and desulfurization comprises the following steps:
s1, inputting recycle hydrogen into a recycle hydrogen separating tank to remove liquid, and then dividing the recycle hydrogen into two paths;
s2, one path of the circulating hydrogen with liquid removed in the S1 is subjected to multi-stage treatment, reacts with fresh hydrogen and raw materials for desulfurization and decarburization, reacts with the fresh hydrogen and the raw materials to obtain hydrogenated saturated oil, and is conveyed to a second mixer, the other path of the circulating hydrogen is subjected to pressure increase by a circulating hydrogen compressor to obtain unpurified circulating hydrogen, and the unpurified circulating hydrogen is conveyed to the second mixer, specifically:
one path of the liquid-removed recycle hydrogen in the S1 is sequentially subjected to H removal through a purification tank2S, PSA apparatus for removing CO and CO2Then, the hydrogen and the fresh hydrogen are boosted by a fresh hydrogen compressor to obtain purified recycle hydrogen which is input into a first mixer; mixing the purified recycle hydrogen with the raw materials in a first mixer, heating the mixture by a heat exchanger, conveying the mixture into a first reactor for hydrogenation saturation reaction to obtain hydrogenated saturated oil, conveying the hydrogenated saturated oil to a second mixer, and boosting the pressure of the other path by a recycle hydrogen compressor to obtain unpurified recycle hydrogen, and conveying the unpurified recycle hydrogen to the second mixer;
and S3, mixing the hydrogenated saturated oil obtained in the S2 and unpurified recycle hydrogen in a second mixer, heating by a heating device, sequentially entering a second reactor for hydrodemetallization reaction, and a third reactor for hydrodeoxygenation and hydrodesulfurization reaction, and finally obtaining a hydrogenation product.
Preferably, in S2, when the activity of the catalyst in the first reactor is reduced, the heat exchanger is heated, a switch on one side of the recycle hydrogen compressor is opened to communicate with the first mixer, so that the unpurified recycle hydrogen is heated by the heat exchanger and then is conveyed to the first reactor to carry out on-line sulfidation on the catalyst bed layer, thereby recovering the activity of the catalyst.
Preferably, the recycle hydrogen in S1 is obtained by using a cold high-molecular technique.
Preferably, the H is removed in the purification tank in S2 by adopting molecular sieve adsorption2S。
Preferably, the raw material in S2 is waste animal and vegetable oil.
Preferably, the new hydrogen in S2 is produced by methanol cracking.
Compared with the prior art, the recycle hydrogen device for solving the contradiction between decarburization and desulfurization provided by the invention has the advantages that the purified recycle hydrogen and fresh hydrogen are adopted in the first reactor, the CO content is below 20ppm, the carbonylation reaction with metal nickel in the catalyst to generate nickel carbonyl is avoided, and the service life of the catalyst is not reduced; due to the second inverseThe reaction temperature of the reactor and the third reactor is high and is far away from the carbonylation reaction temperature zone, so that the carbonylation reaction can not occur although the circulating hydrogen contains CO; because the circulating hydrogen contains H2S is used as a sulfur source for on-line vulcanization of the catalyst, so that the consumption of a sulfur supplement agent is reduced, and H in tail gas is reduced2The content of S reduces the environmental protection pressure; because the recycle hydrogen adopted by the second reactor and the third reactor contains CO and CO2CO and CO in the reaction product2The partial pressure of (a) is increased, so that the effects of inhibiting decarboxylation and decarbonylation are achieved, the selectivity of the deoxidation reaction is improved, and the liquid yield is correspondingly improved.
Drawings
FIG. 1 is a schematic view showing the connection of a recycle hydrogen apparatus for solving the contradiction between decarburization and desulfurization provided in example 1 of the present invention;
FIG. 2 is a flow chart of a method for controlling a hydrogen recycle apparatus for solving the contradiction between decarburization and desulfurization provided in example 2 of the present invention.
Description of the reference numerals
1-recycle hydrogen liquid separation tank, 2-purification tank, 3-PSA device, 4-new hydrogen compressor, 5-recycle hydrogen compressor, 6-first mixer, 7-heat exchanger, 8-first reactor, 9-second mixer, 10-heating device, 11-second reactor, and 12-third reactor.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The embodiment 1 of the invention provides a recycle hydrogen device for solving the contradiction between decarburization and desulfurization, which comprises a recycle hydrogen separation tank 1, wherein the recycle hydrogen separation tank 1 is sequentially connected with a purification tank 2, a PSA device 3, a fresh hydrogen compressor 4, a first mixer 6, a heat exchanger 7, a first reactor 8, a second mixer 9, a heating device 10, a second reactor 11 and a third reactor 12, the recycle hydrogen separation tank 1 is connected with a recycle hydrogen compressor 5, and the recycle hydrogen compressor 5 is respectively connected with the second mixer 9 and the first mixer 6 through a switch.
Thus, with the adoption of the structure, the recycle hydrogen device for solving the contradiction between decarburization and desulfurization is characterized in that recycle hydrogen is input from a recycle hydrogen separating tank 1 to be subjected to liquid removal and then is divided into two paths, wherein one path of the recycle hydrogen is purified by a purifying tank 2 and subjected to pressure swing adsorption by a PSA (pressure swing adsorption) device 3, and is subjected to pressure rise by a fresh hydrogen compressor 4 together with fresh hydrogen to obtain a purified recycle hydrogen first mixer 6, the purified recycle hydrogen is mixed with raw materials in the first mixer 6, is heated by a heat exchanger 7, is conveyed into a first reactor 8 to undergo hydrogenation saturation reaction to obtain hydrogenation saturated oil, is conveyed to a second mixer 9, and the other path of the purified recycle hydrogen is subjected to pressure rise by a recycle hydrogen compressor 5 to obtain unpurified recycle hydrogen and is conveyed to the second mixer 9; after the hydrogenated saturated oil and the unpurified recycle hydrogen are mixed in the second mixer 9, the mixture is heated by a heating device 10 and sequentially enters a second reactor 11 for hydrodemetallization reaction and a third reactor 12 for hydrodeoxygenation and hydrodesulfurization reaction, and finally a hydrogenation product is obtained.
The reaction temperature in the first reactor 8 is 200-240 ℃.
Thus, since the reaction temperature in the first reactor 8 is 200 ℃ to 240 ℃ close to the nickel carbonyl formation temperature of 180 ℃, consideration is given to the problem of CO removal from the recycle hydrogen.
The reaction temperature in the second reactor 11 is 310-360 ℃.
Thus, since the temperature in the second reactor 11 is 310-360 ℃ which is much higher than the 180 ℃ formation temperature of nickel carbonyl, there is no need to consider the problem of CO removal from the recycle hydrogen.
The reaction temperature in the third reactor 12 is 360-380 ℃.
Thus, since the temperature in the third reactor 12 is 360-380 deg.C
Thus, the recycle hydrogen device for solving the contradiction between decarburization and desulfurization is obtained by dividing recycle hydrogen into two paths after liquid is input and removed from a recycle hydrogen separating tank 1, wherein one path is purified by a purifying tank 2 and pressure swing adsorption by a PSA device 3 in sequence, and is boosted by a fresh hydrogen compressor 4 together with fresh hydrogenThe purified recycle hydrogen is mixed with the raw materials in the first mixer 6, heated by a heat exchanger 7 and conveyed into a first reactor 8 for hydrogenation saturation reaction to obtain hydrogenation saturated oil, the hydrogen-oil ratio of the first reactor is ensured to be more than 400:1, and the hydrogenation saturated oil is conveyed to a second mixer 9; the other path is boosted by a recycle hydrogen compressor 5 to obtain unpurified recycle hydrogen which is sent to a second mixer 9 because the recycle hydrogen contains H2S, the requirement of on-line vulcanization of the hydrogenation catalyst is just met, the addition of a sulfur supplement agent is reduced, and the self sulfur balance is realized. After the hydrogenated saturated oil and the unpurified recycle hydrogen are mixed in the second mixer 9, the mixture is heated by a heating device 10 and sequentially enters a second reactor 11 for hydrodemetallization reaction and a third reactor 12 for hydrodeoxygenation and hydrodesulfurization reaction, and finally a hydrogenation product is obtained.
Example 2
As shown in fig. 2, a control method of a hydrogen circulation device based on the solution of contradiction between decarburization and desulfurization includes the following steps:
s1, inputting recycle hydrogen into the recycle hydrogen separating tank 1 to remove liquid, and then dividing the recycle hydrogen into two paths;
s2, one path of the circulating hydrogen with liquid removed in the S1 is subjected to multi-stage treatment, reacts with fresh hydrogen and raw materials for desulfurization and decarburization, reacts with the fresh hydrogen and the raw materials to obtain hydrogenated saturated oil, and is conveyed to the second mixer 9, the other path of the circulating hydrogen is subjected to pressure increase by the circulating hydrogen compressor 5 to obtain unpurified circulating hydrogen, and the unpurified circulating hydrogen is conveyed to the second mixer 9, specifically:
one path of the liquid-removed recycle hydrogen in the S1 is sequentially subjected to H removal through a purification tank 22S, PSA Unit 3 for CO and CO removal2Then, the pressure of the hydrogen and the fresh hydrogen is increased by a fresh hydrogen compressor 4 to obtain purified recycle hydrogen which is input into a first mixer 6; mixing the purified recycle hydrogen with the raw materials in a first mixer 6, heating the mixture by a heat exchanger 7, conveying the mixture into a first reactor 8 for hydrogenation saturation reaction to obtain hydrogenated saturated oil, conveying the hydrogenated saturated oil to a second mixer 9, and increasing the pressure of the other path of the hydrogenated saturated oil by a recycle hydrogen compressor 5 to obtain unpurified recycle hydrogen, and conveying the unpurified recycle hydrogen to the second mixer 9;
and S3, mixing the hydrogenated saturated oil obtained in the S2 and unpurified recycle hydrogen in a second mixer 9, heating the mixture by a heating device 10, and sequentially entering a second reactor 11 for hydrodemetallization reaction and a third reactor 12 for hydrodeoxygenation and hydrodesulfurization reaction to finally obtain a hydrogenation product.
Thus, the control method of the recycle hydrogen device for solving the contradiction between decarburization and desulfurization comprises the steps of inputting recycle hydrogen from a recycle hydrogen separating tank 1 to remove liquid, dividing the recycle hydrogen into two paths, wherein one path of the recycle hydrogen is purified by a purifying tank 2 and a PSA device 3 in sequence, and is subjected to pressure swing adsorption together with new hydrogen by a new hydrogen compressor 4 to obtain a purified recycle hydrogen first mixer 6, mixing the purified recycle hydrogen with raw materials in the first mixer 6, heating by a heat exchanger 7, conveying to a first reactor 8 for hydrogenation saturation reaction to obtain hydrogenation saturated oil, ensuring that the hydrogen-oil ratio of the first reactor is more than 400:1, and conveying to a second mixer 9; the other path is boosted by a recycle hydrogen compressor 5 to obtain unpurified recycle hydrogen which is sent to a second mixer 9 because the recycle hydrogen contains H2S, the requirement of on-line vulcanization of the hydrogenation catalyst is just met, the addition of a sulfur supplement agent is reduced, and the self sulfur balance is realized. After the hydrogenated saturated oil and the unpurified recycle hydrogen are mixed in the second mixer 9, the mixture is heated by a heating device 10 and sequentially enters a second reactor 11 for hydrodemetallization reaction and a third reactor 12 for hydrodeoxygenation and hydrodesulfurization reaction, and finally a hydrogenation product is obtained.
In S2, when the activity of the catalyst in the first reactor 8 is reduced, the heat exchanger 7 is heated, the switch on the side of the recycle hydrogen compressor 5 is opened to communicate with the first mixer 6, so that the unpurified recycle hydrogen is heated by the heat exchanger 7 and then is conveyed to the first reactor 8 to carry out on-line sulfidation on the catalyst bed layer, and the activity of the catalyst is recovered.
Thus, a jumper is led behind the recycle hydrogen compressor (unpurified recycle hydrogen) to be connected with the first mixer 6, when the activity of the catalyst in the first reactor 8 is reduced in the process of changing from a sulfuration state to an oxidation state and the reaction temperature is increased to 240 ℃, the switch of the unpurified recycle hydrogen jumper is opened, the catalyst bed layer in the first reactor 8 is subjected to online sulfuration operation, and the activity of the catalyst is recovered. As the reaction temperature is 240 ℃ far away from the reaction temperature of carbonylation 180 ℃, CO in unpurified circulating hydrogen can not react with metallic nickel in the catalyst to generate nickel carbonyl.
The circulating hydrogen in the S1 is obtained by adopting a cold high-molecular technique.
Thus, the recycle hydrogen obtained by the cold high-molecular technique can be directly used as a source of the recycle hydrogen and is input into the recycle hydrogen separation tank 1.
H is adsorbed and removed in the purification tank 2 in the S2 by adopting a molecular sieve2S。
Thus, the recycle hydrogen which is removed liquid in the recycle hydrogen separation liquid tank 1 is input into the purification tank 2, and then the molecular sieve in the purification tank 2 is used for absorbing and removing H2S。
The raw material in the S2 is waste animal and vegetable oil.
Thus, by using the control method of the recycle hydrogen device for solving the contradiction between decarburization and desulfurization, the contradiction between recycle hydrogen decarburization and catalyst sulfur balance of the waste animal and vegetable oil hydrodeoxygenation device can be solved.
The new hydrogen in S2 is produced by methanol cracking.
Thus, the fresh hydrogen produced by the methanol cracking method and the purified recycle hydrogen can be input into the first mixer 6 after being boosted by the fresh hydrogen compressor 4.
According to the control method of the circulating hydrogen device for solving the contradiction between decarburization and desulfurization, the first reactor adopts purified circulating hydrogen and new hydrogen, the CO content is below 20ppm, the circulating hydrogen and new hydrogen cannot be subjected to carbonylation with metal nickel in a catalyst to generate nickel carbonyl, and the service life of the catalyst cannot be reduced; because the reaction temperature of the second reactor and the third reactor is high and is far away from the carbonylation reaction temperature zone, the carbonylation reaction can not occur although the circulating hydrogen contains CO; because the circulating hydrogen contains H2S is used as a sulfur source for on-line vulcanization of the catalyst, so that the consumption of a sulfur supplement agent is reduced, and H in tail gas is reduced2The content of S reduces the environmental protection pressure; because the recycle hydrogen adopted by the second reactor and the third reactor contains CO and CO2CO and CO in the reaction product2The partial pressure of (A) is increased, and thus the effects of inhibiting decarboxylation and decarbonylation are achieved, and the decarbonylation is improvedThe selectivity of oxygen reaction and the liquid yield are correspondingly improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The utility model provides a solve decarbonization and desulfurization contradictory recycle hydrogen device, its characterized in that, it includes recycle hydrogen divides the fluid reservoir (1), recycle hydrogen divides the fluid reservoir (1) to connect gradually purifying tank (2), PSA device (3), new hydrogen compressor (4), first blender (6), heat exchanger (7), first reactor (8), second blender (9), heating device (10), second reactor (11) and third reactor (12), recycle hydrogen divides fluid reservoir (1) to connect recycle hydrogen compressor (5), recycle hydrogen compressor (5) are connected second blender (9) respectively and are connected first blender (6) through the switch.
2. The apparatus for solving the contradiction between decarburization and desulfurization as set forth in claim 1, wherein the reaction temperature in the first reactor (8) is 200-240 ℃.
3. The apparatus for solving the contradiction between decarburization and desulfurization as set forth in claim 2, wherein the reaction temperature in the second reactor (11) is 310-360 ℃.
4. The apparatus for solving the contradiction between decarburization and desulfurization as set forth in claim 3, wherein the reaction temperature in the third reactor (12) is 360-380 ℃.
5. A control method of a recycle hydrogen device for solving the contradiction between decarburization and desulfurization based on any one of claims 1 to 4, characterized by comprising the steps of:
s1, inputting the recycle hydrogen into a recycle hydrogen liquid separation tank (1) to remove liquid and then dividing the recycle hydrogen into two paths;
s2, one path of the circulating hydrogen with liquid removed in the S1 is subjected to multi-stage treatment, desulfurization and decarburization and then reacts with new hydrogen and raw materials to obtain hydrogenated saturated oil, the hydrogenated saturated oil is conveyed to a second mixer (9), and the other path of the circulating hydrogen is subjected to pressure increase by a circulating hydrogen compressor (5) to obtain unpurified circulating hydrogen, and the unpurified circulating hydrogen is conveyed to the second mixer (9);
and S3, mixing the hydrogenated saturated oil obtained in the S2 and unpurified recycle hydrogen in a second mixer (9), heating the mixture by a heating device (10), and sequentially entering a second reactor (11) for hydrodemetallization reaction and a third reactor (12) for hydrodeoxygenation and hydrodesulfurization reaction to finally obtain a hydrogenation product.
6. The method as claimed in claim 5, wherein in step S2, one of the liquid-removed recycle hydrogen streams in step S1 is desulfurized and decarbonized in a multi-stage process, and then reacted with fresh hydrogen and raw material to obtain hydrogenated saturated oil, which is sent to the second mixer (9), specifically:
one path of the liquid-removed recycle hydrogen in the S1 is sequentially subjected to H removal through a purification tank (2)2S, PSA apparatus (3) for removing CO and CO2Then, the pressure of the hydrogen and the fresh hydrogen is increased by a fresh hydrogen compressor (4) to obtain purified recycle hydrogen which is input into a first mixer (6); and the purified recycle hydrogen is mixed with the raw materials in a first mixer (6), heated by a heat exchanger (7), conveyed into a first reactor (8) for hydrogenation saturation reaction to obtain hydrogenation saturated oil, and conveyed to a second mixer (9).
7. The method for controlling a recycle hydrogen device to solve the contradiction between decarburization and desulfurization according to claim 6, wherein in step S2, when the activity of the catalyst in the first reactor (8) is reduced, the temperature of the heat exchanger (7) is raised, the switch on the recycle hydrogen compressor (5) side is opened to communicate with the first mixer (6), so that the unpurified recycle hydrogen is heated by the heat exchanger (7) and then is sent to the first reactor (8) to carry out on-line sulfidation on the catalyst bed layer, and the activity of the catalyst is recovered.
8. The method as claimed in claim 7, wherein the recycle hydrogen in S1 is obtained by cold high-pressure separation technique.
9. The method for controlling a recycle hydrogen unit to solve the contradiction between decarburization and desulfurization according to claim 8, wherein molecular sieve adsorption is used to remove H in the purification tank (2) in S22S。
10. The method as claimed in any one of claims 5 to 9, wherein the raw material of S2 is waste animal and vegetable oil, and the fresh hydrogen of S2 is produced by methanol cracking.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010234368.XA CN111411025A (en) | 2020-03-30 | 2020-03-30 | Hydrogen circulation device for solving contradiction between decarburization and desulfurization and control method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010234368.XA CN111411025A (en) | 2020-03-30 | 2020-03-30 | Hydrogen circulation device for solving contradiction between decarburization and desulfurization and control method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111411025A true CN111411025A (en) | 2020-07-14 |
Family
ID=71489397
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010234368.XA Pending CN111411025A (en) | 2020-03-30 | 2020-03-30 | Hydrogen circulation device for solving contradiction between decarburization and desulfurization and control method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111411025A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120053377A1 (en) * | 2007-12-20 | 2012-03-01 | Exxonmobil Research And Engineering Company | Multi-stage co-processing of biofeeds for manufacturing of diesel range hydrocarbons |
| CN102504866A (en) * | 2011-11-08 | 2012-06-20 | 海南临高化工实业有限公司 | Method for preparing biodiesel by mixing waste edible oil with mineral diesel oil and hydrogenization |
| CN102942957A (en) * | 2012-10-30 | 2013-02-27 | 中国石油化工股份有限公司 | Presulfuration technology of hydrogenation unit |
| US20160053183A1 (en) * | 2014-08-25 | 2016-02-25 | Uop Llc | Methods for hydrogen sulfide recycling using selective solvents in the hydroprocessing of renewable feedstocks |
| US20180112142A1 (en) * | 2016-10-20 | 2018-04-26 | Iogen Corporation | Method and system for providing upgraded biogas |
-
2020
- 2020-03-30 CN CN202010234368.XA patent/CN111411025A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120053377A1 (en) * | 2007-12-20 | 2012-03-01 | Exxonmobil Research And Engineering Company | Multi-stage co-processing of biofeeds for manufacturing of diesel range hydrocarbons |
| CN102504866A (en) * | 2011-11-08 | 2012-06-20 | 海南临高化工实业有限公司 | Method for preparing biodiesel by mixing waste edible oil with mineral diesel oil and hydrogenization |
| CN102942957A (en) * | 2012-10-30 | 2013-02-27 | 中国石油化工股份有限公司 | Presulfuration technology of hydrogenation unit |
| US20160053183A1 (en) * | 2014-08-25 | 2016-02-25 | Uop Llc | Methods for hydrogen sulfide recycling using selective solvents in the hydroprocessing of renewable feedstocks |
| US20180112142A1 (en) * | 2016-10-20 | 2018-04-26 | Iogen Corporation | Method and system for providing upgraded biogas |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108998106B (en) | Desulfurization and deamination method for coking plant | |
| CN104560132A (en) | Method for hydrotreatment of continuous liquid-phase wax oil | |
| KR20100030595A (en) | Improved hydrotreatment process | |
| CN105505550A (en) | Method for carrying out regeneration treatment on useless lubricating oil | |
| CN104096462B (en) | Yellow phosphorus tail gas purification method | |
| CN1418937A (en) | Method for indudstrialized refining liquefied petrolium gas (LPG) | |
| CN103446861A (en) | Circulating treatment method for regenerated waste gas produced in temperature swing adsorption desulfurization | |
| CN113293024B (en) | Method for preparing biodiesel by three-stage selective hydrodeoxygenation | |
| CN102633232A (en) | Hydrogen generation process and system in float glass manufacturing | |
| CN101372628B (en) | Method for producing clean fuel oil and high-purity chemical products from calcium carbide tail gas | |
| CN111411025A (en) | Hydrogen circulation device for solving contradiction between decarburization and desulfurization and control method thereof | |
| JP2004511623A (en) | Two-stage hydrogenation and stripping of diesel fuel oil in a single reactor | |
| CN111876205B (en) | Gas hydrogenation catalyst vulcanization and vulcanization waste gas treatment and discharge process | |
| CN104099127A (en) | Distillate oil hydrotreating process | |
| CN104045057B (en) | A kind of Sweet natural gas catalyzing part oxidation produces the technique of direct sponge iron | |
| CN103773474B (en) | A kind of gas phase, liquid-phase mixing hydrogenation method | |
| CN107337178B (en) | Process for recycling PSA desorption gas and catalytic regeneration flue gas of oil refinery | |
| CN107537590B (en) | Low-purity hydrogen reduction method for hydrocarbon steam conversion catalyst | |
| CN111115660A (en) | Treatment method for resource utilization of coking desulfurization waste liquid | |
| CN1069915C (en) | Process for hydrogen prodn. and hydrogenating feed gas for ammonia synthesis | |
| CN117582797A (en) | Deep purification process for tail gas of calcium carbide furnace | |
| CN111849550A (en) | Processing technology for reducing sulfur content of light aromatic hydrocarbon | |
| CN114425460B (en) | Regeneration method of deactivated hydrogenation catalyst | |
| JPS6189294A (en) | Method of purifying coke oven gas | |
| CN114410337B (en) | Method and device for producing hydrocarbon-based biofuel by hydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220119 Address after: 334000 sulfur chemical park office, Xiangtun Industrial Park, Dexing City, Shangrao City, Jiangxi Province Applicant after: Jiangxi zunchuang Energy Co.,Ltd. Address before: 518000 Room 201, building A, No. 1, Qian Wan Road, Qianhai Shenzhen Hong Kong cooperation zone, Shenzhen, Guangdong (Shenzhen Qianhai business secretary Co., Ltd.) Applicant before: Shenzhen Taili Energy Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200714 |
|
| WD01 | Invention patent application deemed withdrawn after publication |