CN102850173A - Method for preparing cyclopentane from ethylene cracking C9 heavy fraction - Google Patents
Method for preparing cyclopentane from ethylene cracking C9 heavy fraction Download PDFInfo
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Abstract
The invention relates to a method for preparing cyclopentane from an ethylene cracking C9 heavy fraction. The method comprises the following steps: 1, preheating the ethylene cracking C9 heavy fraction, and depolymerizing to obtain a gas phase material; 2, depolymerizing the gas phase material to obtain crude methylcyclopentadiene and crude cyclopentadiene at the tower top; 3, carrying out monomer separation refining of the crude cyclopentadiene and the crude methylcyclopentadiene to obtain high-purity cyclopentadiene at the tower top; and 4, mixing the high-purity cyclopentadiene with a solvent and hydrogen, allowing the obtained mixture to enter a fixed bed catalyst bed layer, and carrying out a catalytic hydrogenation reaction. The preparation method provided by the invention, which adopts the cracking C9 heavy fraction as a depolymerization raw material, has the advantages of low cost, low equipment requirement, and suitableness for large-scale production; and in the invention, the cyclopentadiene yield is greater than 95%, the cyclopentadiene conversion rate is about 100%, the cyclopentane selectivity is greater than 99%, the cyclopentane yield is greater than 95%, and the purity of the obtained cyclopentane is greater than 99%.
Description
Technical field
The invention belongs to the preparation field of pentamethylene, particularly a kind of method that from nine last running of cracking of ethylene carbon, prepares pentamethylene.
Background technology
Pentamethylene is used for replacing atmospheric ozone layer is had the Chlorofluorocarbons (CFCs) (CFCS) of destruction as the foaming agent as hard polyurethane foams, now has been widely used in producing the fields such as freon-free refrigerator, refrigerator-freezer industry and freezer, pipeline insulation.Along with closing on of the forbidding of the pacts such as Montreal regulations, ODS time limit, CFCS and HCFCS series products are soon with disabled, and pentamethylene will become the leading role in polyurethane foams field.Its reaction formula is as follows:
In Chinese patent CN1321625A, CM1417178A, CN1911875A, all disclose with dicyclopentadiene (DCPD) depolymerization and generated cyclopentadiene, carried out the preparation method that the industrialization continuous hydrogenation is produced pentamethylene.When adopting dicyclopentadiene to carry out depolymerization, a large amount of polymerization lossess of dicyclopentadiene can be made, also the reactor coking and blocking can be caused.The yield of its pentamethylene is lower, only has about 80%.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method for preparing pentamethylene from nine last running of cracking of ethylene carbon; the method is simple to operate; be divided into the depolymerization raw material with cracking carbon nine double distilleds; cost is low; less demanding to equipment; be fit to large-scale production, the purity of the pentamethylene that obtains is greater than 99%.
A kind of method for preparing pentamethylene from nine last running of cracking of ethylene carbon of the present invention comprises:
(1) nine last running of cracking of ethylene carbon are preheated to 120 ~ 150 ℃ after, carry out depolymerization, the depolymerization temperature is 170 ~ 250 ℃, operating pressure is 0.03 ~ 0.3MPa, the residence time is 1.5 ~ 3h, gets gaseous phase materials;
(2) with the further depolymerization of above-mentioned gaseous phase materials, tower top temperature is 70 ~ 110 ℃, and the tower reactor temperature is at 200 ~ 220 ℃, and working pressure is 0.03 ~ 0.3MPa, and reflux ratio is 0.5 ~ 3, obtains thick methyl cyclopentadiene and thick cyclopentadiene in cat head;
(3) it is refining above-mentioned thick cyclopentadiene and thick methyl cyclopentadiene to be carried out monomer separation, and monomer separation cat head end is 40 ~ 60 ℃, and the temperature of tower reactor is at 140 ~ 170 ℃, system pressure position 0.02 ~ 0.2MPa, and reflux ratio is 1 ~ 4, cat head obtains high-purity cyclopentadiene;
(4) with above-mentioned cyclopentadiene with enter the fixed bed catalyst bed after solvent, hydrogen mix and carry out catalytic hydrogenation reaction and get final product; Wherein used catalyzer is Ni-Pa-γ-Al in the shortening
2O
3Composite catalyst is with γ-Al
2O
3Be carrier, take Ni-Pa as the catalyst activity component, wherein the mass content of Ni-Pa is 0.3 ~ 1%; The mass ratio of described cyclopentadiene and solvent is 1:5 ~ 10, and the mol ratio of cyclopentadiene and hydrogen is 1:3.5 ~ 4.5, and the hydrogenation system temperature is 35 ~ 65 ℃, and system pressure is 1.0 ~ 2.0MPa.
Depolymerization temperature described in the step (1) is 220～250 ℃, operating pressure 0.08 ~ 0.1MPa.
In the further depolymerization described in the step (2), tower top temperature is 100～110 ℃, and the tower reactor temperature is 200 ~ 210 ℃, operating pressure 0.08 ~ 0.1MPa.
Monomer separation cat head end described in the step (3) is 50～60 ℃, and the tower reactor temperature is 160 ~ 170 ℃, and reflux ratio is 2 ~ 4.
Ni-Pa-γ-Al described in the step (4)
2O
3The preparation method of composite catalyst is, with γ-Al
2The O carrier is immersed in 5 ~ 10h in Ni, the Pa soluble salt solution, and filtering what obtain catalyzer dry 4h obtains in the situation that nitrogen exists is exactly Ni-Pa-γ-Al
2O
3Composite catalyst.
The described Ni-Pa-γ-Al of step (4)
2O
3The mass content of Ni is that the mass content of 0.1 ~ 0.4%, Pa is 0.2 ~ 0.6% in the composite catalyst
The described Ni-Pa-γ-Al of step (4)
2O
3In the composite catalyst, the mass content of Ni-Pa is 0.4 ~ 0.8%.
Solvent described in the step (4) is alcoholic solvent.
Above-mentioned alcoholic solvent is methyl alcohol, ethanol, tertiary amyl alcohol or the trimethyl carbinol.
The hydrogenation system temperature is 40～60 ℃ in the catalytic hydrogenation reaction described in the step (4), and system pressure is 1.0～1.5MPa; The mass ratio of cyclopentadiene and solvent is 1:5 ~ 8, and the mol ratio of cyclopentadiene and hydrogen is 1:3.5 ~ 4.
The heat exchange mode that fixed bed described in the step (4) adopts inner heat exchange, jacket for heat exchange to combine with the outer loop heat exchange.Fixed bed bottom extraction hydrogenation products, hydrogenation products cools off through water cooler, and a part is returned mixing tank and is carried out circulating cooling, and the refining pentamethylene that obtains is removed in a part of extraction.
The present invention assigns to replace existing pentamethylene hydrogenating materials with cracking carbon nine double distilleds, thereby improves the yield of pentamethylene, a large amount of losses of raw material when overcoming dicyclopentadiene as the raw material depolymerization; The present invention adopts more rational heat-exchange equipment and ring hot mode.Can effectively remove hydrogenation reaction heat, stop cyclopentadiene to generate dicyclopentadiene; The present invention adopts novel pentamethylene hydrogenation catalyst, and hydrogenation is carried out under lower temperature, shortens the hydrogenation residence time, and cyclopentadiene generates dicyclopentadiene when overcoming high temperature hydrogenation.
Exist the dimer of a large amount of dicyclopentadiene, cyclopentadiene and methyl cycle pentadiene dimer, cyclopentadiene and styrenic in the middle of nine last running of cracking carbon, the present invention is divided into the depolymerization raw material with cracking carbon nine double distilleds, can utilize fully the cyclopentadiene in its component, the yield of cyclopentadiene reaches 95%, thereby improve the yield of pentamethylene, a large amount of losses of raw material when overcoming DCPD as the raw material depolymerization.
Hydrogenation fixed-bed reactor of the present invention adopt inner heat exchange, jacket for heat exchange to combine with the outer loop heat exchange.Can effectively remove hydrogenation reaction heat, stop cyclopentadiene production dicyclopentadiene.
The present invention adopts Ni-Pa-γ-Al
2O
3Composite catalyst can make hydrogenation carry out under lower temperature, shortens the hydrogenation residence time, and cyclopentadiene generates dicyclopentadiene when overcoming hydrogenation.
The technology of the present invention cyclopentadiene yield is greater than 95%, and the cyclopentadiene transformation efficiency is about 100%, and the pentamethylene selectivity is greater than 99%, and the pentamethylene yield obtains the purity of pentamethylene greater than 99% greater than 95%.
Beneficial effect
(1) preparation method of the present invention is simple to operate, is divided into the depolymerization raw material with cracking carbon nine double distilleds, and cost is low, and less demanding to equipment is fit to large-scale production;
(2) cyclopentadiene (CPD) yield is greater than 95% among the present invention, and the cyclopentadiene transformation efficiency is about 100%, and the pentamethylene selectivity is greater than 99%, and the pentamethylene yield obtains the purity of pentamethylene greater than 99% greater than 95%.
Description of drawings
Fig. 1 is device of the present invention and schema;
E1 is preheater, E2, E3 are respectively water cooler, R1 is the depolymerization still, V1 is the hydrogenation mixing tank, and T1 is cleavage column, and T2 is the monomer separation tower, T3 is that (inner heat exchange is with in the inside to the fixed bed catalyst bed reactor, the outside is jacket for heat exchange), C1 is liquid distributing groove, P1, P2, P3 are material-handling pump.F1～F7 is that material related among the present invention: F1 is that nine last running of cracking carbon, F2 are that gaseous phase materials, the F3 of depolymerization reaction be thick cyclopentadiene with gas phase mixture, the F4 of thick methyl cyclopentadiene is that highly purified cyclopentadiene, F5 are pentamethylene behind the hydrogenation that hydrogenation solvent, F6 are the pentamethylene that returns by supercooler of hydrogenation, F7 is extraction, and F8 is hydrogen.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Following table 1 is that cracking of ethylene carbon nine main compound form
Table 1
The raw material extraction process:
Cracking of ethylene by-product C 9 fraction is under 10～25kpa at working pressure, and obtaining boiling point through underpressure distillation cutting is that 160～215 ℃ component is the present invention and uses material carbon nine last running.Its moiety sees Table 2
Nine last running of table 2 cracking carbon form
The technical process of each case study on implementation of the present invention as shown in Figure 1.
Embodiment 1
Carbon nine raw material last running enter depolymerization among the depolymerization still R1 after preheater E1 is preheated to 120 ℃, the depolymerization temperature is 170 ℃, and operating pressure is 0.05MPa, and the residence time is 1.5h; The gaseous phase materials F2 that generates enters cleavage column T1, tower top temperature is 70 ℃, the tower reactor temperature is at 200 ℃, working pressure is 0.03MPa, reflux ratio is 0.5, the compound F3 of the thick cyclopentadiene that cat head obtains and thick methyl cyclopentadiene, gas phase enters monomer separation tower T2, monomer separation cat head end is 40 ℃, and the temperature of tower reactor is at 140 ℃, system pressure position 0.05MPa, reflux ratio is 2, the highly purified cyclopentadiene that cat head obtains enters mixing tank V1 after water cooler E2 cooling, mix by 1:7 and hydrogen mol ratio 1:4 with the t-butanol solvent mass ratio, enters by liquid distributing groove C1 Ni-Pa(Ni:Pa=1:2 is housed) content 0.6%Ni-Pa-γ-Al
2O
3Composite catalyst bed fixed-bed reactor T3 carries out hydrogenation reaction under 40 ℃, reaction pressure is 1.3MPa.Hydrogenation products is after water cooler E3 cooling, and a part is returned mixing tank, and a part of extraction is to hydrogenated products tank V1, and the ratio of returning material and extraction material is 4:1.
Hydrogenator T3 is 50L, and loaded catalyst is 25kg.The hydrogenated products of extraction carry out the pentamethylene purity detecting with gas-chromatography, can reach 99% through refining pentamethylene purity, and what obtain the results are shown in Table 3.
Embodiment 2
Carbon nine raw material last running enter depolymerization among the depolymerization still R1 after preheater E1 is preheated to 130 ℃, the depolymerization temperature is 220 ℃, and operating pressure is 0.10MPa, and the residence time is 2h; The gaseous phase materials F2 that generates enters cleavage column T1, tower top temperature is 100 ℃, the tower reactor temperature is at 210 ℃, working pressure is 0.2MPa, reflux ratio is 2, the compound F3 of the thick cyclopentadiene that cat head obtains and thick methyl cyclopentadiene, gas phase enters monomer separation tower T2, monomer separation cat head end is 50 ℃, and the temperature of tower reactor is at 150 ℃, system pressure position 0.10MPa, reflux ratio is 3, the highly purified cyclopentadiene that cat head obtains enters mixing tank V1 through the cold E2 of water cooler after but, mixes by 1:7 and hydrogen mol ratio 1:4 with the alcohol solvent mass ratio, enters by liquid distributing groove C1 Ni-Pa(Ni:Pa=1:2 is housed) content 0.6%Ni-Pa-γ-Al
2O
3Composite catalyst bed fixed-bed reactor T3 carries out hydrogenation reaction under 40 ℃, reaction pressure is 1.3MPa.Hydrogenation products is after water cooler E3 cooling, and a part is returned mixing tank, and a part of extraction is to hydrogenated products tank V1, and the ratio of returning material and extraction material is 4:1.
Hydrogenator is 50L, and loaded catalyst is 25kg.The hydrogenated products of extraction carry out the pentamethylene purity detecting with gas-chromatography, can reach 99% through refining pentamethylene purity, and what obtain the results are shown in Table 3.
Embodiment 3
Carbon nine raw material last running enter depolymerization among the depolymerization still R1 after preheater E1 is preheated to 150 ℃, the depolymerization temperature is 200 ℃, and operating pressure is 0.2MPa, and the residence time is 3h; The gaseous phase materials F2 that generates enters cleavage column T1, tower top temperature is 100 ℃, the tower reactor temperature is at 220 ℃, working pressure is 0.3MPa, reflux ratio is 3, the compound F3 of the thick cyclopentadiene that cat head obtains and thick methyl cyclopentadiene, gas phase enters monomer separation tower T2, monomer separation cat head end is 60 ℃, and the temperature of tower reactor is at 160 ℃, system pressure position 0.08MPa, reflux ratio is 4, the highly purified cyclopentadiene that cat head obtains enters mixing tank V1 after water cooler E2 cooling, mix than by 1:7 and hydrogen mol ratio 1:4 with the tertiary amyl alcohol solvent quality, enters by liquid distributing groove C1 Ni-Pa(Ni:Pa=1:2 is housed) content 0.6%Ni-Pa-γ-Al
2O
3Composite catalyst bed fixed-bed reactor T3 carries out hydrogenation reaction under 40 ℃, reaction pressure is 1.3MPa.Hydrogenation products is after water cooler E3 cooling, and a part is returned mixing tank, and a part of extraction is to hydrogenated products tank V1, and the ratio of returning material and extraction material is 4:1.
Hydrogenator is 50L, and loaded catalyst is 25kg.The hydrogenated products of extraction carry out the pentamethylene purity detecting with gas-chromatography, can reach 99% through refining pentamethylene purity, and what obtain the results are shown in Table 3.
Embodiment 4
Carbon nine raw material last running enter depolymerization among the depolymerization still R1 after preheater E1 is preheated to 150 ℃, the depolymerization temperature is 220 ℃, and operating pressure is 0.05MPa, and the residence time is 1.5h; The gaseous phase materials F2 that generates enters cleavage column T1, tower top temperature is 110 ℃, the tower reactor temperature is at 220 ℃, working pressure is 0.3MPa, reflux ratio is 0.5, the compound F3 of the thick cyclopentadiene that cat head obtains and thick methyl cyclopentadiene, gas phase enters monomer separation tower T2, and monomer separation cat head end is 60 ℃, and the temperature of tower reactor is at 170 ℃, system pressure position 0.2MPa, reflux ratio is 1, and the highly purified cyclopentadiene that cat head obtains enters mixing tank V1 after water cooler E2 cooling, mix by 1:7 and hydrogen mol ratio 1:4 with the t-butanol solvent mass ratio, enter by liquid distributing groove C1 Ni-Pa(Ni:Pa=1:3 be housed) content 0.4%, Ni-Pa-γ-Al
2O
3Composite catalyst bed fixed-bed reactor T3 carries out hydrogenation reaction under 40 ℃, reaction pressure is 1.3MPa.Hydrogenation products is after water cooler E3 cooling, and a part is returned mixing tank, and a part of extraction is to hydrogenated products tank V1, and the ratio of returning material and extraction material is 4:1.
Hydrogenator is 50L, and loaded catalyst is 25kg.The hydrogenated products of extraction carry out the pentamethylene purity detecting with gas-chromatography, can reach 99% through refining pentamethylene purity, and what obtain the results are shown in Table 3.
Embodiment 5
Carbon nine raw material last running enter depolymerization among the depolymerization still R1 after preheater E1 is preheated to 120 ℃, the depolymerization temperature is 250 ℃, and operating pressure is 0.3MPa, and the residence time is 3h; The gaseous phase materials F2 that generates enters cleavage column T1, tower top temperature is 100 ℃, the tower reactor temperature is at 220 ℃, working pressure is 0.03MPa, reflux ratio is 3, the compound F3 of the thick cyclopentadiene that cat head obtains and thick methyl cyclopentadiene, gas phase enters monomer separation tower T2, monomer separation cat head end is 50 ℃, the temperature of tower reactor is at 160 ℃, system pressure position 0.02MPa, reflux ratio is 1, gas phase enters the monomer separation tower, the highly purified cyclopentadiene that cat head obtains enters mixing tank V1 after water cooler E2 cooling, mix than by 1:7 and hydrogen mol ratio 1:4 with the tertiary amyl alcohol solvent quality, enter by liquid distributing groove C1 Ni-Pa(Ni:Pa=1:2 is housed) content 0.8%, Ni-Pa-γ-Al
2O
3Composite catalyst bed fixed-bed reactor T3 carries out hydrogenation reaction under 40 ℃, reaction pressure is 1.3MPa.Hydrogenation products is after water cooler E3 cooling, and a part is returned mixing tank V1, and a part of extraction is to the hydrogenated products tank, and the ratio of returning material and extraction material is 4:1.
Hydrogenator is 50L, and loaded catalyst is 25kg.The hydrogenated products of extraction carry out the pentamethylene purity detecting with gas-chromatography, can reach 99% through refining pentamethylene purity, and what obtain the results are shown in Table 3.
Embodiment 6
Carbon nine raw material last running enter depolymerization among the depolymerization still R1 after preheater E1 is preheated to 150 ℃, the depolymerization temperature is 200 ℃, and operating pressure is 0.2MPa, and the residence time is 2h; The gaseous phase materials F2 that generates enters cleavage column T1, tower top temperature is 100 ℃, the tower reactor temperature is at 220 ℃, working pressure is 0.3MPa, reflux ratio is 3, the compound F3 of the thick cyclopentadiene that cat head obtains and thick methyl cyclopentadiene, gas phase enters monomer separation tower T2, and monomer separation cat head end is 50 ℃, and the temperature of tower reactor is at 170 ℃, system pressure position 0.05MPa, reflux ratio is 3, and the highly purified cyclopentadiene that cat head obtains enters mixing tank V1 after water cooler E2 cooling, mix than by 1:5 and hydrogen mol ratio 1:4 with the tertiary amyl alcohol solvent quality, enter by liquid distributing groove C1 Ni-Pa(Ni:Pa=1:2 be housed) content 0.6%, Ni-Pa-γ-Al
2O
3Composite catalyst bed fixed-bed reactor T3 carries out hydrogenation reaction under 40 ℃, reaction pressure is 1.3MPa.Hydrogenation products is after water cooler E3 cooling, and a part is returned mixing tank, and a part of extraction is to hydrogenated products tank V1, and the ratio of returning material and extraction material is 4:1.
Hydrogenator is 50L, and loaded catalyst is 25kg.The hydrogenated products of extraction carry out the pentamethylene purity detecting with gas-chromatography, can reach 99% through refining pentamethylene purity, and what obtain the results are shown in Table 3.
Embodiment 7
Carbon nine raw material last running enter depolymerization among the depolymerization still R1 after preheater E1 is preheated to 140 ℃, the depolymerization temperature is 230 ℃, and operating pressure is 0.3MPa, and the residence time is 2.5h; The gaseous phase materials F2 that generates enters cleavage column T1, tower top temperature is 90 ℃, the tower reactor temperature is at 210 ℃, working pressure is 0.3MPa, reflux ratio is 2.5, the compound F3 of the thick cyclopentadiene that cat head obtains and thick methyl cyclopentadiene, gas phase enters monomer separation tower T2, and monomer separation cat head end is 50 ℃, and the temperature of tower reactor is at 160 ℃, system pressure position 0.1MPa, reflux ratio is 2, and the highly purified cyclopentadiene that cat head obtains enters mixing tank V1 after water cooler E2 cooling, mix than by 1:10 and hydrogen mol ratio 1:4 with the tertiary amyl alcohol solvent quality, enter by liquid distributing groove C1 Ni-Pa(Ni:Pa=1:2 be housed) content 0.6%, Ni-Pa-γ-Al
2O
3Composite catalyst bed fixed-bed reactor T3 carries out hydrogenation reaction under 40 ℃, reaction pressure is 1.3MPa.Hydrogenation products is after water cooler E3 cooling, and a part is returned mixing tank, and a part of extraction is to hydrogenated products tank V1, and the ratio of returning material and extraction material is 4:1.
Hydrogenator is 50L, and loaded catalyst is 25kg.The hydrogenated products of extraction carry out the pentamethylene purity detecting with gas-chromatography, can reach 99% through refining pentamethylene purity, and what obtain the results are shown in Table 3.
Embodiment 8
Carbon nine raw material last running enter depolymerization among the depolymerization still R1 after preheater E1 is preheated to 140 ℃, the depolymerization temperature is 240 ℃, and operating pressure is 0.08MPa, and the residence time is 3h; The gaseous phase materials F2 that generates enters cleavage column T1, tower top temperature is 110 ℃, the tower reactor temperature is at 220 ℃, working pressure is 0.2MPa, reflux ratio is 1.5, the compound F3 of the thick cyclopentadiene that cat head obtains and thick methyl cyclopentadiene, gas phase enters monomer separation tower T2, and monomer separation cat head end is 50 ℃, and the temperature of tower reactor is at 160 ℃, system pressure position 0.2MPa, reflux ratio is 2, and the highly purified cyclopentadiene that cat head obtains enters mixing tank V1 after water cooler E2 cooling, mix by 1:7 and hydrogen mol ratio 1:4 with the t-butanol solvent mass ratio, enter by liquid distributing groove C1 Ni-Pa(Ni:Pa=1:2 be housed) content 0.6%, Ni-Pa-γ-Al
2O
3Composite catalyst bed fixed-bed reactor T3 carries out hydrogenation reaction under 35 ℃, reaction pressure is 1.3MPa.Hydrogenation products is after water cooler E3 cooling, and a part is returned mixing tank, and a part of extraction is to hydrogenated products tank V1, and the ratio of returning material and extraction material is 4:1.
Hydrogenator is 50L, and loaded catalyst is 25kg.The hydrogenated products of extraction carry out the pentamethylene purity detecting with gas-chromatography, can reach 99% through refining pentamethylene purity, and what obtain the results are shown in Table 3.
Embodiment 9
Carbon nine raw material last running enter depolymerization among the depolymerization still R1 after preheater E1 is preheated to 120 ℃, the depolymerization temperature is 190 ℃, and operating pressure is 0.3MPa, and the residence time is 1.5h; The gaseous phase materials F2 that generates enters cleavage column T1, tower top temperature is 110 ℃, the tower reactor temperature is at 220 ℃, working pressure is 0.10MPa, reflux ratio is 1.5, the compound F3 of the thick cyclopentadiene that cat head obtains and thick methyl cyclopentadiene, gas phase enters monomer separation tower T2, and monomer separation cat head end is 40 ℃, and the temperature of tower reactor is at 160 ℃, system pressure position 0.2MPa, reflux ratio is 1, and the highly purified cyclopentadiene that cat head obtains enters mixing tank V1 after water cooler E2 cooling, mix by 1:7 and hydrogen mol ratio 1:4 with the t-butanol solvent mass ratio, enter by liquid distributing groove C1 Ni-Pa(Ni:Pa=1:2 be housed) content 0.6%, Ni-Pa-γ-Al
2O
3Composite catalyst bed fixed-bed reactor T3 carries out hydrogenation reaction under 50 ℃, reaction pressure is 1.3MPa.Hydrogenation products is after water cooler E3 cooling, and a part is returned mixing tank, and a part of extraction is to hydrogenated products tank V1, and the ratio of returning material and extraction material is 4:1.
Hydrogenator is 50L, and loaded catalyst is 25kg.The hydrogenated products of extraction carry out the pentamethylene purity detecting with gas-chromatography, can reach 99% through refining pentamethylene purity, and what obtain the results are shown in Table 3.
Each case study on implementation result of table 3
| Title | CPD depolymerization rate (%) | CPD turnover ratio (%) | CPD selection rate (%) | Pentamethylene yield (%) |
| Case study on implementation 1 | 96.23 | 99.95 | 99.63 | 96.52 |
| Case study on implementation 2 | 95.62 | 99.89 | 99.68 | 95.02 |
| Case study on implementation 3 | 95.14 | 99.91 | 99.24 | 95.68 |
| Case study on implementation 4 | 94.32 | 99.56 | 98.15 | 94.23 |
| Case study on implementation 5 | 95.38 | 99.65 | 99.53 | 95.45 |
| Case study on implementation 6 | 96.12 | 99.03 | 98.68 | 94.23 |
| Case study on implementation 7 | 94.63 | 99.41 | 99.22 | 95.62 |
| Case study on implementation 8 | 95.32 | 99.92 | 99.19 | 96.05 |
| Case study on implementation 9 | 95.34 | 99.62 | 97.86 | 93.69 |
Annotate: 1.CPD depolymerization rate refers to that DCPD depolymerization production CPD amount accounts for the per-cent of CPD in the raw material.
2.CPD the CPD that transformation efficiency reacts away when referring to the CPD hydrogenation accounts for the per-cent of hydrogenating materials CPD.
3.CPD selection rate refers to that amount that CPD is converted to pentamethylene accounts for the per-cent of hydrogenating materials CPD.
4. the pentamethylene yield refers to that the pentamethylene that obtains after refining accounts for the per-cent of hydrogenating materials CPD.
Claims (10)
1. method for preparing pentamethylene from nine last running of cracking of ethylene carbon comprises:
(1) nine last running of cracking of ethylene carbon are preheated to 120 ~ 150 ℃ after, carry out depolymerization, the depolymerization temperature is 170 ~ 250 ℃, operating pressure is 0.03 ~ 0.3MPa, the residence time is 1.5 ~ 3h, gets gaseous phase materials;
(2) with the further depolymerization of above-mentioned gaseous phase materials, tower top temperature is 70 ~ 110 ℃, and the tower reactor temperature is at 200 ~ 220 ℃, and working pressure is 0.03 ~ 0.3MPa, and reflux ratio is 0.5 ~ 3, obtains thick methyl cyclopentadiene and thick cyclopentadiene in cat head;
(3) it is refining above-mentioned thick cyclopentadiene and thick methyl cyclopentadiene to be carried out monomer separation, and tower top temperature is 40 ~ 60 ℃, and the tower reactor temperature is at 140 ~ 170 ℃, system pressure position 0.02 ~ 0.2MPa, and reflux ratio is 1 ~ 4, cat head obtains high-purity cyclopentadiene;
(4) with above-mentioned cyclopentadiene with enter the fixed bed catalyst bed after solvent, hydrogen mix and carry out catalytic hydrogenation reaction and get final product; Wherein used catalyzer is Ni-Pa-γ-Al in the shortening
2O
3Composite catalyst is with γ-Al
2O
3Be carrier, take Ni-Pa as the catalyst activity component, wherein the mass content of Ni-Pa is 0.3 ~ 1%; The mass ratio of described cyclopentadiene and solvent is 1:5 ~ 10, and the mol ratio of cyclopentadiene and hydrogen is 1:3.5 ~ 4.5, and the hydrogenation system temperature is 35 ~ 65 ℃, and system pressure is 1.0 ~ 2.0MPa.
2. a kind of method for preparing pentamethylene from nine last running of cracking of ethylene carbon according to claim 1, it is characterized in that: the depolymerization temperature described in the step (1) is 220～250 ℃, operating pressure 0.08 ~ 0.1MPa.
3. a kind of method that from nine last running of cracking of ethylene carbon, prepares pentamethylene according to claim 1, it is characterized in that: in the further depolymerization described in the step (2), tower top temperature is 100～110 ℃, and the tower reactor temperature is 200 ~ 210 ℃, operating pressure 0.08 ~ 0.1MPa.
4. a kind of method that from nine last running of cracking of ethylene carbon, prepares pentamethylene according to claim 1, it is characterized in that: the tower top temperature described in the step (3) is 50～60 ℃, and the tower reactor temperature is 160 ~ 170 ℃, and reflux ratio is 2 ~ 4.
5. a kind of method for preparing pentamethylene from nine last running of cracking of ethylene carbon according to claim 1 is characterized in that: the described Ni-Pa-γ-Al of step (4)
2O
3The mass content of Ni is that the mass content of 0.1 ~ 0.4%, Pa is 0.2 ~ 0.6% in the composite catalyst
6. a kind of method for preparing pentamethylene from nine last running of cracking of ethylene carbon according to claim 1 is characterized in that: the described Ni-Pa-γ-Al of step (4)
2O
3In the composite catalyst, the mass content of Ni-Pa is 0.4 ~ 0.8%.
7. a kind of method for preparing pentamethylene from nine last running of cracking of ethylene carbon according to claim 1, it is characterized in that: the solvent described in the step (4) is alcoholic solvent.
8. a kind of method for preparing pentamethylene from nine last running of cracking of ethylene carbon according to claim 7, it is characterized in that: described alcoholic solvent is methyl alcohol, ethanol, tertiary amyl alcohol or the trimethyl carbinol.
9. a kind of method that from nine last running of cracking of ethylene carbon, prepares pentamethylene according to claim 1, it is characterized in that: the hydrogenation system temperature is 40～60 ℃ in the catalytic hydrogenation reaction described in the step (4), system pressure is 1.0～1.5MPa; The mass ratio of cyclopentadiene and solvent is 1:5 ~ 8, and the mol ratio of cyclopentadiene and hydrogen is 1:3.5 ~ 4.
10. a kind of method for preparing pentamethylene from nine last running of cracking of ethylene carbon according to claim 1 is characterized in that: the heat exchange mode that the fixed bed described in the step (4) adopts inner heat exchange, jacket for heat exchange to combine with the outer loop heat exchange.
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| CN105399590A (en) * | 2015-10-22 | 2016-03-16 | 恒河材料科技股份有限公司 | Method for preparing dicyclopentadiene through gas-liquid phase depolymerization of C9 raw material |
| CN109265305A (en) * | 2018-10-24 | 2019-01-25 | 濮阳市联众兴业化工有限公司 | A method of cracking nine low temperature hydrogenation preparing cyclopentane of carbon |
| CN114805001A (en) * | 2021-01-20 | 2022-07-29 | 本田技研工业株式会社 | Preparation device and preparation method of renewable cyclopentane |
| CN115043699A (en) * | 2022-07-15 | 2022-09-13 | 辽宁北化鲁华化工有限公司 | Method for preparing high-purity dicyclopentadiene through industrial cracking carbon nine |
| CN115974638A (en) * | 2023-03-21 | 2023-04-18 | 新疆天利石化股份有限公司 | Method for producing high-purity cyclopentane by cracking carbon nine |
| CN116082113A (en) * | 2023-03-13 | 2023-05-09 | 新疆天利石化股份有限公司 | Method for producing high-purity cyclopentane and methylcyclopentane by hydrogenating nine light components of carbon |
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| CN105399590A (en) * | 2015-10-22 | 2016-03-16 | 恒河材料科技股份有限公司 | Method for preparing dicyclopentadiene through gas-liquid phase depolymerization of C9 raw material |
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| CN109265305B (en) * | 2018-10-24 | 2020-01-07 | 濮阳市联众兴业化工有限公司 | Method for preparing cyclopentane by low-temperature hydrogenation of cracking carbon nine |
| CN114805001A (en) * | 2021-01-20 | 2022-07-29 | 本田技研工业株式会社 | Preparation device and preparation method of renewable cyclopentane |
| CN114805001B (en) * | 2021-01-20 | 2024-02-02 | 本田技研工业株式会社 | Preparation device and preparation method of renewable cyclopentane |
| CN115043699A (en) * | 2022-07-15 | 2022-09-13 | 辽宁北化鲁华化工有限公司 | Method for preparing high-purity dicyclopentadiene through industrial cracking carbon nine |
| CN116082113A (en) * | 2023-03-13 | 2023-05-09 | 新疆天利石化股份有限公司 | Method for producing high-purity cyclopentane and methylcyclopentane by hydrogenating nine light components of carbon |
| CN115974638A (en) * | 2023-03-21 | 2023-04-18 | 新疆天利石化股份有限公司 | Method for producing high-purity cyclopentane by cracking carbon nine |
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