CN1049001C - Hydrogenation refinement of reformate - Google Patents
Hydrogenation refinement of reformate Download PDFInfo
- Publication number
- CN1049001C CN1049001C CN97118845A CN97118845A CN1049001C CN 1049001 C CN1049001 C CN 1049001C CN 97118845 A CN97118845 A CN 97118845A CN 97118845 A CN97118845 A CN 97118845A CN 1049001 C CN1049001 C CN 1049001C
- Authority
- CN
- China
- Prior art keywords
- bromine
- aromatics
- oil
- raw material
- hydrofining
- 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.)
- Expired - Lifetime
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 22
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract 2
- 238000000605 extraction Methods 0.000 abstract description 6
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 7
- 238000007670 refining Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910003296 Ni-Mo Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 125000001246 bromo group Chemical class Br* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
一种重整生成油的加氢精制工艺，采用已脱除大于C9芳烃的重整生成油，其中芳烃含量一般在20～85重%，溴价0.5～8.0克溴/100克为原料。加氢精制反应条件为：反应温度150～200℃，反应器中氢分压0.5～3.0兆帕，液体空速3～15时-1，体积氢油比100～500。采用的加氢催化剂为条状薄壳型Pd/γ-Al2O3。其中Pd含量在0.15～0.6重%之间。加氢精制生成油的溴价远远低于芳烃抽提装置对原料0.2克溴/100克的要求，并且在加氢过程中芳烃没有损失。由于已脱除重组分，所用的催化剂无需再生可以使用三年以上。A hydrofining process for reformed oil, using reformed oil from which aromatics greater than C9 have been removed, wherein the aromatics content is generally 20-85% by weight, and the bromine value is 0.5-8.0g bromine/100g as raw material. The hydrofining reaction conditions are: reaction temperature 150-200°C, hydrogen partial pressure in the reactor 0.5-3.0 MPa, liquid space velocity 3-15 h -1 , volume hydrogen-oil ratio 100-500. The hydrogenation catalyst used is strip thin-shell Pd/γ-Al 2 O 3 . Wherein the Pd content is between 0.15 and 0.6% by weight. The bromine price of the oil produced by hydrofining is far lower than the requirement of 0.2g bromine/100g raw material for the aromatics extraction unit, and there is no loss of aromatics during the hydrogenation process. Since heavy components have been removed, the catalyst used can be used for more than three years without regeneration.
Description
The present invention is that a kind of this hydrofining technology is particularly suitable for the hydrogenation and removing of small amounts of olefins in the extractive reformed oil of aromatic hydrocarbons to containing the hydrofining technology of alkene in the aromatic type gasoline, and aromatic hydrocarbons does not wherein have the hydrogen loss of adding.
The reformed oil that petroleum naphtha is produced through catalytic reforming contains a large amount of aromatic hydrocarbons and alkane and small amounts of olefins, if this reformed oil is used to produce aromatic hydrocarbons, this part alkene must be removed to satisfy the requirement of production high purity aromatic hydrocarbons.Traditional technology is to use vulcanized Co-Mo, the Ni-Mo catalyst hydrogenation is refining or acidic white earth refining with adsorbents.Co-Mo, Ni-Mo catalyst hydrogenation process for refining since its temperature of reaction height (300～320 ℃), refining effect poor, emit SO when aromatic hydrocarbons has loss, sulfide type catalyst regeneration
2Make expensive shortcomings such as reforming catalyst poisoning, new device does not re-use.Problem producers such as acidic white earth refining with adsorbents technology life cycle is lacked, need frequently be changed, useless carclazyte contaminate environment are reluctant to use.The Chinese patent CN86108622 that we have authorized adopts the bromine valency to be, 0.5～8.0 gram bromine/100 grams, aromaticity content be the reformed oil of 35～55% (weight percents) as raw material, used a kind of thin shell type Pd/ γ-Al
2O
3Be used for technology that recapitalization generating oil hydrogenation removes alkene and eliminated the shortcoming of above-mentioned two kinds of technologies basically, more than 200 ℃, generally about 260 ℃, the alkene deep removal in the reformed oil, aromatic hydrocarbons loses less than 0.5%.But CN 86108622 described technologies are at the hydrofining without the full cut reformed oil that takes off heavy constituent.Because a small amount of high boiling fraction that Pintsch process generates in the reforming process can be adsorbed on catalyst surface by force when being lower than 200 ℃, accumulation causes catalyst deactivation gradually.So the hydrogenation technique of CN 86108622 need be in the operation down of comparatively high temps (200～300 ℃), bigger volume of hydrogen oil ratio (500), so that high boiling component, prolongs catalyzer work-ing life from the catalyst surface desorption.
It is low that goal of the invention of the present invention provides a kind of service temperature, and the volume of hydrogen oil ratio is low, catalyzer long service life and need not the regenerated hydrofining technology for reformed oil.
Hydrofining technology of the present invention is characterized in that the reformed oil as aromatics extraction raw material, has removed high boiling heavy aromatics.For the BTX extraction process, boiling point is higher than C
9Aromatic hydrocarbons be not more than 8% (weight percent).For the benzene extraction process, only contain benzene and small amount of toluene.Total aromaticity content is 20～85% (weight percents) in the extracting raw material, bromine valency 0.5～8.0 gram bromine/100 grams.150～200 ℃ of temperature of reaction, hydrogen dividing potential drop 0.5～3.0 MPa in the reactor, liquid air speed are 3～15 o'clock
-1, hydrogen to oil volume ratio is 100～500.
Identical among the catalyst P d content that the present invention adopts and the CN 86108622, be 0.15～0.6 weight %, carrier is commercially available γ-Al
2O
3, right cylinder strip, 1.2～2.8 centimetres of cross section diameters, 130～300 meters of specific surfaces
2/ gram, 0.3～0.6 milliliter/gram of pore volume.The Preparation of catalysts method is identical with normal thin shell mould noble metal catalyst, and its step is referring to USP2475155.
The present invention compared with prior art has the following advantages:
1, technology is simple, service temperature is low, the volume of hydrogen oil ratio is low.
2, alkene deep removal, aromatic hydrocarbons does not almost have the hydrogen loss of adding.
3, catalyzer need not regeneration, long service life.
Embodiments of the invention are as follows:
Embodiment 1
Raw material is the reformed oil after taking off the heavies column fractionation, and the aromatic hydrocarbons total content is 68.78% (weight percent, down together), and wherein benzene content is 10.34%, and toluene is 24.56%, C
8Aromatic hydrocarbons is 30.77%, C
9Aromatic hydrocarbons is 3.11%, and the bromine valency is 3.35 gram bromines/100 grams.Use contains the Pd/ γ-Al of palladium 0.3% (weight)
2O
3The thin shell type catalyzer carries out the hydrofining test in 100 milliliters of riser reactors, it the results are shown in Table 1.
As can be seen from Table 1, temperature of reaction 150～260 ℃, reaction pressure 1.0～2.3 MPas, volume of hydrogen oil ratio 100～400, the liquid air speed is at 2～15 o'clock
-1Between when changing, product bromine valency is far below the index requests of 0.2 gram bromine/100 grams, and aromatic hydrocarbons does not add hydrogen loss.
Table 1.
| Reaction conditions | Generate oil analysis | ||||
| Temperature (℃) | Pressure (MPa) | The liquid air speed (time -1) | Hydrogen-oil ratio (volume) | Bromine valency (gram bromine/100 grams) | Total aromatic hydrocarbons (heavy %) |
| 150 | 1.7 | 4 | 200 | 0.0133 | 68.12 |
| 170 | 1.7 | 4 | 200 | 0.0082 | 68.78 |
| 195 | 1.7 | 4 | 200 | 0.0056 | 68.66 |
| 170 | 1.0 | 4 | 200 | 0.0112 | 68.63 |
| 170 | 2.3 | 4 | 200 | 0.0051 | 68.56 |
| 170 | 1.7 | 6 | 200 | 0.0096 | 68.77 |
| 170 | 1.7 | 15 | 200 | 0.021 | 68.50 |
| 170 | 1.7 | 2 | 200 | 0.0032 | 68.33 |
| 170 | 1.7 | 4 | 400 | 0.0047 | 68.24 |
| 170 | 1.7 | 4 | 100 | 0.0135 | 69.12 |
Embodiment 2
The raw material that uses is identical with embodiment 1 with catalyzer, and reaction conditions is: 170～175 ℃ of temperature, pressure 1.7 MPas are during liquid air speed 4
-1, volume of hydrogen oil ratio 200.Table 2 is hydrogenation runs results of 1000 days.
As can be seen from Table 2, under above-mentioned processing condition, catalyzer the running of not regenerating through nearly three years 1000 days, activity has decline slightly, and its result is still within acceptability limit.The afterreaction temperature improved 5 ℃ in 700 days, and bromine value drops to close with the catalyst runs initial stage.Because this moment, the upper limit from temperature of reaction also had a segment distance, catalyzer need not be survived again and can be used for a long time.
Embodiment 3
Be 165 ℃ except that reactor inlet temperatures in the reaction conditions, other is with embodiment 2, and charging is a benzene extraction plant raw material, and total aromaticity content is 30.13%, wherein contains benzene 24.53%, and toluene 5.78%, bromine valency are 2.87 gram bromines/100 grams.Reaction result sees Table 3.
As can be seen from Table 3, catalyzer was through running in 1000 hours, and product bromine valency is well below index request, and not loss of aromatic hydrocarbons.So this catalyzer and technology also are suitable for the hydrofining of benzene extraction plant raw material.
Table 2.
| Product analysis | Remarks | ||
| Runtime (my god) | Bromine valency (gram bromine/100 grams) | Total aromatic hydrocarbons (heavy %) | |
| 1 | 0.0065 | 68.55 | |
| 100 | 0.0078 | 69.03 | |
| 200 | 0.0071 | 68.45 | |
| 300 | 0.0082 | 68.56 | |
| 400 | 0.0077 | 67.95 | |
| 500 | 0.0096 | 69.10 | |
| 600 | 0.017 | 68.65 | |
| 700 | 0.026 | 69.05 | Temperature of reaction rises to 175 ℃ from 170 |
| 800 | 0.0088 | 68.76 | |
| 900 | 0.0085 | 67.99 | |
| 1000 | 0.011 | 68.32 | |
Table 3.
| Product analysis | ||
| Runtime (hour) | Bromine valency (gram bromine/100 grams) | Total aromatic hydrocarbons (heavy %) |
| 10 | 0.0036 | 30.23 |
| 100 | 0.0045 | 29.99 |
| 200 | 0.0041 | 31.05 |
| 300 | 0.0032 | 30.45 |
| 400 | 0.0047 | 30.19 |
| 500 | 0.0056 | 29.87 |
| 600 | 0.0048 | 30.56 |
| 700 | 0.0036 | 30.72 |
| 800 | 0.0038 | 30.11 |
| 900 | 0.0045 | 30.55 |
| 1000 | 0.0041 | 30.21 |
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97118845A CN1049001C (en) | 1997-10-24 | 1997-10-24 | Hydrogenation refinement of reformate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97118845A CN1049001C (en) | 1997-10-24 | 1997-10-24 | Hydrogenation refinement of reformate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1210131A CN1210131A (en) | 1999-03-10 |
| CN1049001C true CN1049001C (en) | 2000-02-02 |
Family
ID=5175007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97118845A Expired - Lifetime CN1049001C (en) | 1997-10-24 | 1997-10-24 | Hydrogenation refinement of reformate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1049001C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014044195A1 (en) | 2012-09-21 | 2014-03-27 | 中国石油化工股份有限公司 | Reformate hydrotreatment method |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088089C (en) * | 1999-10-13 | 2002-07-24 | 中国石油化工集团公司 | Process for hydrogenating raw material of hydrocarbon |
| CN102911721B (en) * | 2012-11-15 | 2015-02-11 | 中国海洋石油总公司 | Method for removing olefins from reformate through liquid phase circulation selective hydrogenation |
| CN104342200B (en) * | 2013-08-09 | 2016-05-11 | 中国石油天然气股份有限公司 | A method for selective hydrogenation of reformed oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1019221B (en) * | 1988-11-12 | 1992-11-25 | 约瑟夫·梅厄 | Clamp for connecting templates |
| CN1109495A (en) * | 1994-03-28 | 1995-10-04 | 中国石油化工总公司 | Rifining method for catalylic cracking gasoline by adding hydrogen |
| CN1157315A (en) * | 1996-02-13 | 1997-08-20 | 荆门石油化工研究院 | One section series hydrogenation refining process |
-
1997
- 1997-10-24 CN CN97118845A patent/CN1049001C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1019221B (en) * | 1988-11-12 | 1992-11-25 | 约瑟夫·梅厄 | Clamp for connecting templates |
| CN1109495A (en) * | 1994-03-28 | 1995-10-04 | 中国石油化工总公司 | Rifining method for catalylic cracking gasoline by adding hydrogen |
| CN1157315A (en) * | 1996-02-13 | 1997-08-20 | 荆门石油化工研究院 | One section series hydrogenation refining process |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014044195A1 (en) | 2012-09-21 | 2014-03-27 | 中国石油化工股份有限公司 | Reformate hydrotreatment method |
| EP2899253A4 (en) * | 2012-09-21 | 2016-06-29 | China Petroleum & Chemical | PROCESS FOR HYDROTREATING REFORMAT |
| RU2609780C2 (en) * | 2012-09-21 | 2017-02-03 | Чайна Петролиум Энд Кемикл Корпорейшн | Reformate hydrotreatment method and apparatus |
| US9879186B2 (en) | 2012-09-21 | 2018-01-30 | China Petroleum & Chemical Corporation | Reformate hydrotreatment method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1210131A (en) | 1999-03-10 |
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| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Karamay Konka Chemical Co., Ltd. Assignor: Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences Contract record no.: 2010650000007 Denomination of invention: Hydrogenation refinement of reformate Granted publication date: 20000202 License type: Exclusive License Open date: 19990310 Record date: 20100527 |
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| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20000202 |