CN1184136C - Method for preparing high purity hydrogen by catalyzing dry gas being as raw material - Google Patents
Method for preparing high purity hydrogen by catalyzing dry gas being as raw material Download PDFInfo
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- CN1184136C CN1184136C CNB011344237A CN01134423A CN1184136C CN 1184136 C CN1184136 C CN 1184136C CN B011344237 A CNB011344237 A CN B011344237A CN 01134423 A CN01134423 A CN 01134423A CN 1184136 C CN1184136 C CN 1184136C
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- 239000007789 gas Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 22
- 239000001257 hydrogen Substances 0.000 title claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000002994 raw material Substances 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001179 sorption measurement Methods 0.000 claims abstract description 8
- 239000006227 byproduct Substances 0.000 claims abstract description 7
- 230000009466 transformation Effects 0.000 claims abstract description 7
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 5
- 230000008859 change Effects 0.000 claims abstract description 4
- 150000001336 alkenes Chemical class 0.000 claims description 25
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 10
- 238000006477 desulfuration reaction Methods 0.000 claims description 7
- 230000023556 desulfurization Effects 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 238000004523 catalytic cracking Methods 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- -1 comprise shortening Substances 0.000 claims description 2
- 238000004904 shortening Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 239000003610 charcoal Substances 0.000 abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract 1
- 238000004220 aggregation Methods 0.000 abstract 1
- 238000005336 cracking Methods 0.000 abstract 1
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 235000003599 food sweetener Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010094 polymer processing Methods 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 239000003765 sweetening agent Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a method for preparing high purity hydrogen by using catalyzing dry gas as a raw material, which is characterized in that a byproduct which is dry gas of a catalyzing cracking device in an oil refinery is used as a raw material, which greatly widens the range of hydrogen preparing raw materials; Simultaneously, two stages of catalytic hydrogenation reaction processes are adopted by the present invention to purify geed gas, wherein in a first stage of hydrogenation reaction, a row tube type reactor is adopted, which can not be limited by the temperature difference of a tube and a shell side. A novel titanium oxide base hydrogenation catalyst which has low activity temperature and high charcoal aggregation resistance capability and has certain tolerance to oxygen is contained in the reactor. Industrial hydrogen with the purity which is larger than 99.5% can be finally obtained through the processes of ZnO devulcanization, water vapor conversion, intermediate temperature transformation and pressure change adsorption after hydrogenation.
Description
Technical field
The present invention relates to produce with the refinery by-product gas method of high-purity hydrogen, is the method that raw material is produced high-purity hydrogen with the catalytic cracking unit by-product gas particularly.
Background technology
Containing saturated or a certain amount of unsaturated and by-product gas alkene with refinery is that the raw material of producing hydrogen generally adopts at home.Because in hydrogen production process, conversion catalyst has strict demand to alkene in the raw material and total sulfur, otherwise will cause conversion catalyst knot charcoal and poisoning, and saturated and organosulfur is converted into inorganic sulfur and removes with ZnO then the way that therefore adopts hydrogenation mostly with alkene.But alkene be hydrogenated to strong exothermal reaction, its temperature rise of per 1% alkene is about 23～25 ℃, and is so too high as olefin(e) centent in the unstripped gas, will cause reactor and bed temperature superelevation and can't normal running.The measure that solves has two kinds: first kind is that the olefin(e) centent in the feeding gas is limited in certain scope, specific implementation method one is as patent ZL95 1 08811.4, adopting the coking dry gas is raw material, both reached the purpose of utilizing manufacture gas, bed temperature is controlled in the normal operating restraint, but this technology still have certain limitation to the composition of charging; The 2nd, as patent CN1075740A, hydrogenation reaction is carried out in charging, the compressed machine Returning reactor inlet of the reaction product of a part is with the olefin(e) centent in the dilution feeding gas, this technology investment expense height, energy consumption height, flow process complexity.Second kind as patent CN1200397A, partial reaction heat is removed by isothermal reactor earlier, and then continue to finish the reaction that alkene and organosulfur transform at second adiabatic reactor, this technology is limited in 20% to the content of alkene in the charging, otherwise easily cause overtemperature, therefore as adopt the gases such as catalysis drying gas of olefin(e) centent＞20%, need be used with the lower unstripped gas of other olefin(e) centents.In addition, the temperature difference between the strict limiter tube shell side of the structure of isothermal reactor is not more than 50 ℃, thereby structure is comparatively complicated, and cost is higher, and open, operation downtime is also comparatively complicated.
Summary of the invention
The object of the present invention is to provide a kind of catalysis drying gas with refinery catalytic cracking unit's by-product is raw material, adopts the two-stage hydrogenation reaction process that unstripped gas is carried out the method that purifying treatment is produced high-purity hydrogen.
For achieving the above object, the present invention is the method that raw material is produced high-purity hydrogen with the catalysis drying gas, comprise shortening, ZnO desulfurization, water vapor conversion, middle temperature transformation and pressure-swing adsorption process, its principal feature is that with refinery catalytic cracking unit's by-product dry gas be raw material, adopt the two-stage catalytic hydrogenation reaction process that unstripped gas is carried out purifying treatment, its concrete steps comprise:
(1) two-stage catalytic hydrogenation reaction, temperature is 180～400 ℃, and pressure is 1.5～3.5MPa, and air speed is 500～1500 o'clock
-1
(2) ZnO desulfurization, temperature of reaction are 200～350 ℃, and pressure is 1.5～3.5MPa;
(3) unstripped gas after refining carries out conversion reaction through water vapor in converter;
(4) pyrolytic conversion gas carries out the middle temperature transformation reaction after UTILIZATION OF VESIDUAL HEAT IN;
(5) become air cooling in and but be the high-purity technical hydrogen more than 99.5% after the pressure-swing adsorption process processing can obtain purity.
Describe the characteristics of the inventive method in detail below in conjunction with accompanying drawing.
Description of drawings
Fig. 1 is the process flow diagram of the inventive method.
Embodiment
As shown in Figure 1, boost through unstripped gas press 1 from the catalysis drying gas of refinery catalytic cracking unit, the olefin(e) centent of this unstripped gas below 30% (V), organic sulfur content 100～300ppm, O
2Content 0.5～1.0% (V), N
2Content 10～20% (V), and contain CO, CO
2Deng impurity.Unstripped gas heater via 2 is introduced into one-stage hydrogenation reactor 3 after being heated to about 200 ℃, and alkene in reactor in the unstripped gas and organosulfur are substantially by saturated and conversion.The hydrogenation catalyst that is adopted be a kind of be CO, Mo, the Ni type hydrogenation catalyst of carrier with novel titanium oxide, this catalyst activity temperature is low, stronger resistive connection charcoal ability is arranged and to the tolerance of oxygen, pass through hydrogenation, alkene in the catalysis drying gas (olefin(e) centent allows to reach about 30%) is saturated, oxygen is by the while hydrogenation, and then by two sections additional hydrogenation, organosulfur thoroughly transformed.One-stage hydrogenation reactor 3 adopts shell and tube reactor, and the tubulation diameter is φ 32～φ 60mm, and temperature of reaction is 180～260 ℃, and pressure is 1.5～3.5MPa, and air speed is 500～1500 o'clock
-1, and pipe, the shell side temperature difference are unrestricted.The exit gas of first section hydrogenator 3 enters second section hydrogenator 5 again, this carry out alkene and organosulfur replenish and final hydrogenation reaction, the temperature of reaction of secondary hydrogenation reactor is 260～400 ℃, and pressure is 1.5～3.5MPa, and air speed is 500～1500 o'clock
-1Removed by the saturation water generation steam of shell side by alkene and the saturated reaction heat that produces of oxygen hydrogenation in one-stage hydrogenation reactor 3, thereby keep the stable of tube side bed temperature, 4 is drum among the figure.The exit gas of second section hydrogenator 5 enters ZnO desulphurization reactor 6 again, with the lower ZnO sweetening agent of active temperature with H
2S removes, and temperature of reaction is 200～350 ℃, and pressure is 1.5～3.5MPa, the olefin(e) centent of unstripped gas＜1% (V) after the desulfurization, total sulfur＜0.5ppm.Unstripped gas after refining with after water vapor mixes, carries out conversion reaction in proportion in converter 7.After pyrolytic conversion gas utilized waste heat boiler 8 to produce steam, further reaction in middle temperature transformation reactor 9 became in the gas in the gained and contains 3～6% N
2Gas and CO, CO
2, CH
4Deng impurity.Become in described gas through in become and enter the transformer adsorber 11 that special-purpose sorbent material is housed after 10 heat exchange of gas water cooler are cooled off, in pressure-swing adsorption process, the N of middle change gas
2Gas and CO, CO
2, CH
4Be adsorbed together Deng impurity, thereby acquisition purity is at 99.5% high-purity technical hydrogen.Institute's hydrogen can satisfy the needs of olefine reaction substantially in the catalysis drying gas.
Because adopt technique scheme and technical process, the inventive method has the following advantages:
(1) can utilize catalytic cracked dry gas that refinery all has as hydrogen feedstock, widen the scope of hydrogen feedstock greatly.
(2) the high reaction heat generation water vapor that can utilize hydrogenation of olefins to produce had both relaxed reaction conditions, can reduce power consumption of polymer processing again.
(3) the one-stage hydrogenation reactor of employing application specific architecture, the temperature difference can be unrestricted between its shell journey, helps reducing the cost of reactor, simplifies the shutting down operation greatly.
(4) adopt the lower ZnO sweetening agent of active temperature, hydrogenation and desulfurization reaction temperature are complementary, relaxed operational condition, reduce the device power consumption of polymer processing.
(5) adopt special-purpose sorbent material, with the N in the middle change gas
2Effectively remove, thereby obtain purity at the high-purity technical hydrogen more than 99.5%.
The characteristics of method that the invention is further illustrated by the following examples.
Embodiment
Catalysis drying gas (composition sees Table 1) boosts to 2.0MPa through the catalysis drying gas compressor, and is heated to about 200 ℃, is introduced into first section hydrogenator then, and alkene and organosulfur are substantially by saturated and conversion in the unstripped gas; Reactor outlet gas enters second section hydrogenator again, carries out replenishing and final hydrogenation reaction of alkene and organosulfur at this.Its reaction heat is removed by shell side generation 2.5MPa steam in the one-stage hydrogenation reactor.The gas of secondary hydrogenation reactor outlet enters the ZnO adsorber again with H
2S all removes, alkene＜1% of the unstripped gas after making with extra care, and total sulfur＜0.5ppm, and with H
2O/C is that 3.5/1 ratio is mixed with water vapor through converter and middle temperature transformation reactor and further reacted.Become gas (composition sees Table 2) in the gained, remove wherein contained water vapor after pressure-swing adsorption process is incited somebody to action wherein CO, CO through cooling
2, CH
4, N
2Remove, finally obtaining pressure is that 1.2MPa purity is at the plant hydrogen more than 99.5%.
The composition of table 1 unstripped gas (V%)
| Form | ％ |
| H 2 | 15.91 |
| CO | 1.6 |
| CO 2 | 1.07 |
| N 2 | 18.27 |
| O 2 | 0.34 |
| CH 4 | 26.36 |
| C 2H 4 | 18.73 |
| C 2H 6 | 16.33 |
| C 3H 6 | 1.18 |
| C 3H 8 | 0.14 |
| C 4H 8 | 0.05 |
| C 4H 10 | 0.02 |
| C 5 | / |
| ∑ | 100 |
| ∑ C wherein ＝ | 19.96 |
Become the composition (V%) of gas in the table 2
| Form | ％ |
| CO | 1.7 |
| CO 2 | 18.1 |
| CH 4 | 6.01 |
| N 2 | 4.63 |
| H 2 | 69.56 |
| ∑ | 100 |
Claims (2)
1, a kind of is the method that raw material is produced high-purity hydrogen with the catalysis drying gas, comprise shortening, ZnO desulfurization, water vapor conversion, middle temperature transformation and pressure-swing adsorption process, it is characterized in that with refinery catalytic cracking unit's by-product dry gas be raw material, the volume percent of the olefin(e) centent of described unstripped gas is below 30%, organic S content is 100～300ppm, O
2The volume percent of content is 0.5～1.0%, N
2The volume percent of content is 10～20%, and contains CO and CO
2, adopt the two-stage catalytic hydrogenation reaction process that unstripped gas is carried out purifying treatment, concrete steps comprise:
(1) two-stage catalytic hydrogenation reaction: wherein shell and tube reactor is adopted in the one-stage hydrogenation reaction, and the tubulation diameter is φ 32～φ 60mm, and temperature of reaction is 180～260 ℃, and pressure is 1.5～3.5MPa, and air speed is 500～1500 o'clock
-1, and pipe, the shell side temperature difference are unrestricted; The temperature of reaction of secondary hydrogenation reactor is 260～400 ℃, and pressure is 1.5～3.5MPa, and air speed is 500～1500 o'clock
-1
(2) ZnO desulfurization, temperature of reaction are 200～350 ℃, and pressure is 1.5～3.5MPa, the volume percent of the olefin(e) centent of unstripped gas＜1% after the desulfurization, total sulfur＜0.5ppm;
(3) unstripped gas after refining carries out conversion reaction with water vapor in converter;
(4) pyrolytic conversion gas carries out the middle temperature transformation reaction after UTILIZATION OF VESIDUAL HEAT IN;
(5) become air cooling in and but be the high-purity technical hydrogen more than 99.5% after the pressure-swing adsorption process processing can obtain purity.
2, in accordance with the method for claim 1, become gas after pressure-swing adsorption process in it is characterized in that, can be with 3～6% N in the middle change gas
2Gas and CO, CO
2, CH
4Be adsorbed together, thereby obtain purity at the high-purity technical hydrogen more than 99.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011344237A CN1184136C (en) | 2001-11-01 | 2001-11-01 | Method for preparing high purity hydrogen by catalyzing dry gas being as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011344237A CN1184136C (en) | 2001-11-01 | 2001-11-01 | Method for preparing high purity hydrogen by catalyzing dry gas being as raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1415532A CN1415532A (en) | 2003-05-07 |
| CN1184136C true CN1184136C (en) | 2005-01-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011344237A Expired - Lifetime CN1184136C (en) | 2001-11-01 | 2001-11-01 | Method for preparing high purity hydrogen by catalyzing dry gas being as raw material |
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8664459B2 (en) | 2008-03-31 | 2014-03-04 | Air Products And Chemicals, Inc. | Process for hydrogenating olefins |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408171C (en) * | 2006-08-03 | 2008-08-06 | 湖南泰鑫瓷业有限公司 | Catalyst for hydrogen prodn. by converting methane and carbon dioxide, and method for preparing the same |
| CN101239702B (en) * | 2008-03-18 | 2010-06-23 | 上海大学 | High temperature coke oven crude gas hydrogen generating system device and technique |
| CN106635163B (en) * | 2015-11-02 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of method of coking dry gas preparing ethylene cracking material by hydrogenation |
| CN107987873B (en) * | 2017-11-13 | 2020-10-02 | 盘锦北方沥青燃料有限公司 | Catalytic cracking dry gas olefin conversion and removal method |
-
2001
- 2001-11-01 CN CNB011344237A patent/CN1184136C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8664459B2 (en) | 2008-03-31 | 2014-03-04 | Air Products And Chemicals, Inc. | Process for hydrogenating olefins |
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| Publication number | Publication date |
|---|---|
| CN1415532A (en) | 2003-05-07 |
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Address after: Anhui Beili Anyuan 21 No. 100101 Beijing Chaoyang District City Co-patentee after: Wuhan Branch, Sinopec Corp. Patentee after: Sinopec Engineering Incorporation Co-patentee after: Beijing Haishunde Titanium Catalyst Co., Ltd. Address before: 100011 Beijing City, Xicheng District, No. 67 Andrew Co-patentee before: Wuhan Branch, Sinopec Corp. Patentee before: Engrg Construction Co., SINOPEC Co-patentee before: Beijing Haishunde Titanium Catalyst Co., Ltd. |
|
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20050112 |