CN103772111B - The tail gas catalyzed method of hydrotreating of a kind of rubber plant - Google Patents
The tail gas catalyzed method of hydrotreating of a kind of rubber plant Download PDFInfo
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- CN103772111B CN103772111B CN201210408470.2A CN201210408470A CN103772111B CN 103772111 B CN103772111 B CN 103772111B CN 201210408470 A CN201210408470 A CN 201210408470A CN 103772111 B CN103772111 B CN 103772111B
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Abstract
The present invention discloses the tail gas catalyzed method of hydrotreating of a kind of rubber plant, take tert-butyl catechol as stopper, with loading type Pd/C for catalyzer, the rubber plant's tail gas being rich in alkynes and divinyl is 50-100 DEG C in temperature of reaction, reaction pressure is 1.5-5.0MP, and the volume space velocity of rubber plant's tail gas is 0.5-1.5h
-1, amounts of hydrogen is carry out hydrogenation reaction by beds under the condition of 10-40L/h.The unsaturated hydrocarbons such as the alkynes in rubber plant's tail gas and diolefine can be converted into monoolefine or alkane by the method substantially completely, improve the utilising efficiency of the C4 resource in rubber plant's tail gas.
Description
Technical field
The present invention relates to the tail gas catalyzed method of hydrotreating of a kind of rubber plant, relate in particular to a kind of tail gas catalyzed method of hydrotreating of rubber plant being rich in unsaturated C4 hydrocarbon.
Background technology
The a large amount of C4 hydro carbons of by-product in refining of petroleum and petrochemical production process, fully utilizing it is the necessary means improving Business Economic Benefit, but the domestic utilization to C4 hydro carbons is also in the starting stage at present.
CN201110036915.4 discloses the method for hydrotreating of a kind of unsaturated C4.Reacted by two-stage hydrogenation after unsaturated C4 mixes with hydrogen, gained reactant, after cooling, being separated, obtains saturated C4 product; One-stage hydrogenation reaction conditions is: reaction pressure 2.0-2.3MPa, one-stage hydrogenation reactor inlet temperature 60-90 DEG C, bed temperature 90-120 DEG C, volume space velocity 1.0-3.0h
-1; Secondary hydrogenation reaction conditions is: reaction pressure 2.0-2.3MPa, second-stage hydrogenation reactor temperature in 160-180 DEG C, bed temperature 260-290 DEG C, volume space velocity 1.0-3.0h
-1.The method flow process is simple, easy handling, reaction heat can be made full use of, extending catalyst running period, liquid yield are high.
CN201010204490.9 discloses the selec-tive hydrogenation technique of a kind of high alkynes content C4 logistics, by the C4 logistics containing high density alkynes by one or more fixed bed hydrogenation reactor with circulation line (I), the C4 mixture containing high density alkynes is made under the effect of catalyzer, to remove alkynes by selective hydrogenation reaction and generate divinyl and butylene, again by the end reactor (II) without circulation line, the C4 logistics containing lower concentration alkynes is made to remove remaining alkynes further; Adopt selec-tive hydrogenation technique of the present invention and catalyzer, can process the alkyne concentration of C4 logistics up to 20-50wt%, the alkynes content of C4 logistics after hydrogenation can be down to below 1.5wt%, can be used as the raw material of butadiene extraction unit.C4 logistics can be made to be fully used by this technique, and improve the productive rate of divinyl.
CN201010204491.3 discloses a kind of selec-tive hydrogenation technique of high butadiene content C4 logistics, by the C4 logistics containing high density divinyl by one or more fixed bed hydrogenation reactor with circulation line (I), the C4 mixture containing high density divinyl is made to generate butylene by selective hydrogenation reaction removing divinyl and alkynes under the effect of catalyzer, again by the end reactor (II) without circulation line, the C4 logistics containing lower concentration divinyl is made to remove remaining divinyl and alkynes further; Adopt selec-tive hydrogenation technique of the present invention and catalyzer, the divinyl of C4 logistics and the concentration of carbon four alkynes and scope 5-80wt% can be processed, divinyl and the alkynes content of C4 logistics after hydrogenation can be down to below 10ppm respectively, the selectivity that divinyl generates 1-butylene can reach more than 50%, can be used as the raw material producing 1-butylene.C4 logistics can be made to obtain Appropriate application by this technique.
CN01114177.8 discloses a kind of by C
4cut prepares the Catalysts and its preparation method of liquefied petroleum gas (LPG), and catalyzer is with α-AL
2o
3bead is carrier, is active constituent with palladium, and the palladium on catalyzer adopts electroless plating method and carries, and the specific surface area of catalyzer is 5 ~ 20m
2/ g, pore volume 0.3 ~ 0.5ml/g, bulk density is 0.80 ~ 0.95g/ml, and palladium content is 0.03% ~ 0.5% of total catalyst weight.This catalyzer adopts electroless plating method to carry palladium, and hydrogenation activity component can be made to be plated in catalyst surface very equably, and have catalyst preparation process and simplify, the dispersity of palladium is high, and catalyst hydrogenation activity is high, and running life is long, reduces products production cost.
C4 hydro carbons involved in aforesaid method, mainly for the C 4 fraction in refinery exhaust, such as, is just rich in a large amount of C4 hydro carbons in the tail gas of cracking ethylene preparation device or catalytic cracking unit.The composition being rich in C4 hydrocarbon tail gas is the important factor determining how C 4 fraction utilizes.It is different from the refinery exhaust being rich in C4 hydrocarbon,
The exhaust gas composition being rich in the rubber plant of C4 hydrocarbon is more complicated, and it is the highly undersaturated mixed C4 hydrocarbon of one, alkynes and 1,3-butadiene content all very high, carry out burning or hydrotreatment time easily there is polymerization or coking, impact burning and hydrotreatment effect.
Summary of the invention
In order to effectively utilize the C4 resource in rubber plant's tail gas, the present invention discloses the tail gas catalyzed method of hydrotreating of a kind of rubber plant, the unsaturated hydrocarbons such as the alkynes in rubber plant's tail gas and diolefine can be converted into monoolefine or alkane by the method substantially completely, improve the utilising efficiency of the C4 resource in rubber plant's tail gas.
The tail gas catalyzed method of hydrotreating of a kind of rubber plant, take tert-butyl catechol as stopper, with loading type Pd/C for catalyzer, the rubber plant's tail gas being rich in alkynes and divinyl is 50-100 DEG C in temperature of reaction, reaction pressure is 1.5-5.0MP, and the volume space velocity of rubber plant's tail gas is 0.5-1.5h
-1, amounts of hydrogen is carry out hydrogenation reaction by beds under the condition of 10-40L/h.
The volume content being rich in alkynes and divinyl in rubber plant's tail gas of alkynes and divinyl described in the inventive method is higher than 35%-40%.
Temperature of reaction described in the inventive method is preferably 60-80 DEG C, and reaction pressure is preferably 2.5-4.0MP
The concentration of the stopper tert-butyl catechol added in the inventive method in rubber plant's tail gas is 50-150mg/L, preferred 70-120mg/L.
Loading type Pd/C catalyst described in the inventive method, the weight content of active ingredient Pd is 0.1-0.5%, preferred 0.1-0.3%, and specific surface area is 500-1200m
2/ g, is preferably 800-1000m
2/ g.
Loading type Pd/C catalyst described in the inventive method is being filled out with the laggard luggage of porcelain ring dilution mixture, and the volume ratio (thinning ratio) of the porcelain ring in beds and Pd/C catalyzer is 2-10:1, is preferably 3-8:1.Described porcelain ring comprises Raschig ring, Pall ring, cascade ring, rectangular saddle ring, iso-saddle ring, preferred Raschig ring.
Beds described in the inventive method at least divides two sections of fillings.By the flow direction of rubber plant's tail gas in beds, the porcelain ring in every section and the thinning ratio of loading type Pd/C catalyst taper off trend.
Beds described in the inventive method divides 3 sections of fillings, and the content of the loading type Pd/C catalyst in every section of beds is identical, and along the flow direction of rubber plant's tail gas in beds, every section of thinning ratio is respectively 7-9:1,3.5-5:1,2-3:1.
In the inventive method, catalyzer needs to carry out reduction treatment before use, and reduction temperature is 80 DEG C-120 DEG C.
Compared with prior art, the tail gas catalyzed method of hydrotreating of a kind of rubber plant of the present invention, tool has the following advantages:
1, the inventive method take tert-butyl catechol as stopper, with loading type Pd/C for catalyzer, and coordinate suitable processing condition to carry out hydrotreatment to rubber plant's tail gas, improve the hydrotreatment effect of rubber plant's tail gas, the unsaturated hydrocarbons such as the alkynes in rubber plant's tail gas and diolefine can be converted into monoolefine or alkane substantially completely;
2, adopt in the inventive method there is suitable physical property with cocoanut active charcoal be the loading type Pd/C of carrier as rubber plant's catalyzer for hydrogenation on tail gas, the polyreaction of alkynes in rubber plant's tail gas and diolefine can be reduced, improve device fortune cycle turnover;
3, catalyst segments filling technology is adopted in the inventive method, by the flow direction of rubber plant's tail gas in beds, porcelain ring in every section and the thinning ratio of loading type Pd/C catalyst taper off trend, hydrotreatment effect can be improved further, improve stability, reduce the generation of polyreaction;
4, the inventive method can by the content of the monoolefine in condition control break rubber plant tail gas hydrogenation product and alkane, this hydrogenation products can, as vehicle fuel gas directly or after process further, also can be used for extracting alkene or be used as reaction raw materials.
specific implementation method
The functions and effects of the inventive method are further illustrated below in conjunction with embodiment.But following examples do not form the restriction to the inventive method.
The tail gas of rubber plant is the highly undersaturated mixed C4 hydrocarbon of one, and the concentration of the 1,3-butadiene of autohemagglutination wherein easily occurs close to 30%, the content of the alkynes such as vinylacetylene can up to more than 12%.Rubber plant of the present invention tail gas contains following component: propane 0.72; Propylene 0.32; Trimethylmethane 4.55; Normal butane 4.17; Propadiene 0.33; Positive iso-butylene 38.24; Anti-butylene 4.50; Maleic 3.07; Methylacetylene 3.68; 1,3-butadiene 29.97; 1，2-butadiene 0.38; Ethylacetylene 1.06; Vinylacetylene 9.01, is volume content.
Embodiment 1
Adopt fixed bed hydrogenation reactor, lower charging (from reactor bottom charging), the content of the stopper tert-butyl catechol added in the tail gas of rubber plant is 100mg/L.Catalyst P d/C(gac is coconut husk type) specific surface area be 870m
2/ g, Pd content 0.15w%, consumption is 30ml, and the thinning ratio of porcelain ring and catalyzer is 5:1, and porcelain ring is ceramic raschig rings, and specification (footpath × height × thick, mm) is Φ 3 × 3 × 1.Catalyzer needs to carry out reduction treatment before using, hydrogen reducing at adopting 100 DEG C.Reaction conditions: 60 DEG C, 3.0MPa, 1.0h
-1, amounts of hydrogen is 15L/h.Hydrogenation products uses gas chromatographic analysis after gathering gas sample, the results are shown in Table 1.
Embodiment 2
Adopt fixed bed hydrogenation reactor, lower charging, the content of the stopper tert-butyl catechol added in the tail gas of rubber plant is 80mg/L.The specific surface area of catalyst P d/C is 870m
2/ g, Pd content 0.15w%, consumption is 30ml, point 3 sections of fillings, and the loading type Pd in every section of beds/C(gac is coconut husk type) content of catalyzer is identical, and the thinning ratio of every section of porcelain ring and catalyzer is respectively 8:1,4:1,2.5:1.Porcelain ring is ceramic raschig rings, and specification (footpath × height × thick, mm) is Φ 3 × 3 × 1.Catalyzer needs to carry out reduction treatment before using, hydrogen reducing at adopting 100 DEG C.Reaction conditions: 60 DEG C, 3.0MPa, 1.0h
-1, amounts of hydrogen is 15L/h.Hydrogenation products uses gas chromatographic analysis after gathering gas sample, the results are shown in Table 1.
Embodiment 3
Temperature of reaction is 65 DEG C, and the content of stopper tert-butyl catechol is 130mg/L, and the thinning ratio of every section of porcelain ring and catalyzer is respectively, 9:1,3.5:1,3:1.Other condition is with embodiment 2.
Embodiment 4
Temperature of reaction is 80 DEG C, and air speed is 0.5h
-1, the content of stopper tert-butyl catechol is 70mg/L, and the thinning ratio of every section of porcelain ring and catalyzer is respectively 7:1,5:1,3:1.Other condition is with embodiment 2.
Embodiment 5
Temperature of reaction is 75 DEG C, and air speed is 0.5h
-1, pressure 4.0MPa, other condition is with embodiment 2.
Embodiment 6
The specific surface area of amounts of hydrogen 25L/h, catalyst P d/C is 980m
2/ g, Pd content 0.25w%, other condition is with embodiment 2.
Embodiment 7
The specific surface area of amounts of hydrogen 35L/h, catalyst P d/C is 1020m
2/ g, Pd content 0.35w%, other condition is with embodiment 2.
Embodiment 8
The thinning ratio of every section of porcelain ring and catalyzer is respectively 7:1,5:1,2:1, and other condition is with embodiment 2.
Comparative example 1
Pd/Al
2o
3make catalyzer (Pd0.15w%), the amount that consumption presses active component palladium is identical with the content of palladium used in embodiment 1.Dilute when reaction conditions with embodiment 1.
The hydrogenation reaction result of table 1 embodiment and comparative example
| Product forms | Propane | Propylene+Trimethylmethane | Normal butane | Positive iso-butylene | Trans-butene-2 | Cis-butene-2 | Methylacetylene | 1,3-butadiene | 1，2-butadiene | Ethylacetylene | Vinylacetylene |
| Embodiment 1 | 2.93 | 9.40 | 43.17 | 8.25 | 15.08 | 8.71 | 0.11 | 7.92 | 1.86 | ||
| Embodiment 2 | 2.87 | 8.40 | 51.17 | 8.44 | 17.98 | 8.08 | 0.12 | - | - | - | - |
| Embodiment 3 | 4.53 | 14.05 | 70.14 | 3.02 | 3.15 | 2.56 | 0.03 | - | - | - | - |
| Embodiment 4 | 1.72 | 8.31 | 62.02 | 8.11 | 12.11 | 5.41 | - | - | - | - | - |
| Embodiment 5 | 3.28 | 9.13 | 47.67 | 11.25 | 17.78 | 8.30 | - | 0.20 | - | - | - |
| Embodiment 6 | 3.20 | 7.44 | 52.86 | 8.90 | 16.78 | 8.93 | - | - | - | - | |
| Embodiment 7 | 3.25 | 7.41 | 53.89 | 8.10 | 16.52 | 8.65 | |||||
| Embodiment 8 | 3.01 | 8.28 | 49.85 | 9.70 | 18.52 | 8.36 | |||||
| Comparative example 1 | 1.75 | 10.72 | 9.00 | 26.00 | 10.38 | 6.71 | - | 31.50 | - | - | 1.99 |
Claims (8)
1. the tail gas catalyzed method of hydrotreating of rubber plant, it is characterized in that: take tert-butyl catechol as stopper, with loading type Pd/C for catalyzer, the rubber plant's tail gas being rich in alkynes and divinyl is 50-100 DEG C in temperature of reaction, reaction pressure is 1.5-5.0MPa, and the volume space velocity of rubber plant's tail gas is 0.5-1.5h
-1amounts of hydrogen is carry out hydrogenation reaction by beds under the condition of 10-40L/h, loading type Pd/C catalyst is being filled out with the laggard luggage of porcelain ring dilution mixture, porcelain ring in beds and the thinning ratio of Pd/C catalyzer take volume basis as 2-10:1, and described porcelain ring comprises Raschig ring, Pall ring, cascade ring, rectangular saddle ring, iso-saddle ring.
2. method according to claim 1, is characterized in that: the described volume content being rich in alkynes and divinyl in rubber plant's tail gas of alkynes and divinyl is higher than 35%-40%.
3. method according to claim 1, is characterized in that: described temperature of reaction is 60-80 DEG C, and reaction pressure is 2.5-4.0MPa.
4. method according to claim 1, is characterized in that: the concentration of stopper tert-butyl catechol in rubber plant's tail gas is 50-150mg/L, and the weight content of loading type Pd/C catalyst active ingredient Pd is 0.1-0.5%, and specific surface area is 500-1200m
2/ g.
5. method according to claim 4, is characterized in that: the concentration of stopper tert-butyl catechol in rubber plant's tail gas is 70-120mg/L, and the weight content of loading type Pd/C catalyst active ingredient Pd is 0.1-0.3%, and specific surface area is 800-1000m
2/ g.
6. method according to claim 1, is characterized in that: the porcelain ring in beds and the volume ratio of Pd/C catalyzer are 3-8:1, and porcelain ring is Raschig ring.
7. method according to claim 1 or 5, is characterized in that: described beds at least divides two sections of fillings, and by the flow direction of rubber plant's tail gas in beds, the porcelain ring in every section and the thinning ratio of loading type Pd/C catalyst taper off trend.
8. method according to claim 7, it is characterized in that: described beds divides 3 sections of fillings, the content of the loading type Pd/C catalyst in every section of beds is identical, along the flow direction of rubber plant's tail gas in beds, every section of thinning ratio is respectively 7-9:1,3.5-5:1,2-3:1.
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