CN114436738A - 一种高纯度甲基环戊烯的制备方法 - Google Patents
一种高纯度甲基环戊烯的制备方法 Download PDFInfo
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- ATQUFXWBVZUTKO-UHFFFAOYSA-N 1-methylcyclopentene Chemical compound CC1=CCCC1 ATQUFXWBVZUTKO-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 41
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 17
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- 238000006471 dimerization reaction Methods 0.000 claims abstract description 11
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- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000003054 catalyst Substances 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
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- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 6
- 238000005336 cracking Methods 0.000 claims description 6
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 238000012691 depolymerization reaction Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 208000005374 Poisoning Diseases 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 claims description 4
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- 231100000572 poisoning Toxicity 0.000 claims description 4
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- 150000002431 hydrogen Chemical class 0.000 claims description 3
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- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
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- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
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- QWJWPDHACGGABF-UHFFFAOYSA-N 5,5-dimethylcyclopenta-1,3-diene Chemical compound CC1(C)C=CC=C1 QWJWPDHACGGABF-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种高纯度甲基环戊烯的制备方法,包括:1)双甲基环戊二烯原料进入反应精馏塔,解聚生成甲基环戊二烯;2)甲基环戊二烯和溶剂、氢气混合后进行加氢反应;3)将加氢产物中的微量甲基环戊二烯通过二聚反应脱除;4)物料经甲基环戊烯精制塔进行分离,塔顶得甲基环戊烯。本发明的制备方法以甲基环戊烯为加氢反应的溶剂,采用加氢和二聚反应相结合的方法,在保证良好的加氢反应效果的前提下,可使简化分离精制的过程,降低能耗,并获得含量大于99%的高纯度甲基环戊烯。
Description
技术领域
本发明属于甲基环戊烯的制备技术领域,具体的说,涉及一种以乙烯裂解C9馏分为原料来制备甲基环戊烯的方法,特别是采用选择加氢和二聚反应组合工艺来制备高纯度甲基环戊烯的方法。
背景技术
甲基环戊烯(MCPE)是一种带支链的环状单烯烃,它是非常稀缺的精细化工原料,可用于生产各种杀虫剂、及合成多种高档三聚体高分子材料等。现有技术中制备甲基环戊烯的参考文献不多见,一般化学可行的合成方法不具备经济可行性,目前以甲基环戊二烯(MCPD)选择加氢的方法最具工业化应用前景。
现有典型技术如US 454760,通过环戊二烯(CPD)烷基化,制成甲基环戊二烯,再通过选择加氢制备甲基环戊烯。对于甲基环戊二烯选择性加氢制备甲基环戊烯通常是在溶剂中进行的,如中国专利CN200510028608.6公开了一种由甲基环戊二烯连续加氢制甲基环戊烯的方法,催化剂以γ-Al2O3为载体,以Pd为活性组分。溶剂取自苯、甲苯、环己烷、乙醇、甲醇、叔戊醇或叔丁醇中的任何一种。反应系统压力为0.9~1.5MPa,反应温度为 60~100℃。反应液部分出料、部分外循环。反应热通过外循环反应液移走。该发明工艺方法为液相反应,需回收溶剂,导致流程长,成本高。为此中国专利ZL201210160362.8 采用加氢反应副产物甲基环戊烷为反应溶剂,并结合加氢产物物料组成对甲基环戊烯分离精制流程作改进,保证在良好的加氢反应效果的前提下,简化了溶剂的回收。但由于甲基环戊烷与甲基环戊烯沸点接近,需要较大的回流比才能得到高纯度的产品。另外,由于甲基环戊二烯与甲基环戊烯很难分离,只有甲基环戊二烯转化率达到99.5%以上,使其含量尽可能低,才能得到高纯度的甲基环戊烯产品,在此情况下,MCPD被深度加氢生成甲基环戊烷(MCPA)的副反应通常是难以避免的。
综上所述,现有由甲基环戊二烯加氢制甲基环戊烯的方法均存在上述缺陷。
发明内容
本发明针对现有技术的不足,提供了一种以乙烯裂解C9馏分(即主要为双甲基环戊二烯)为原料来制备高纯度甲基环戊烯的方法。本发明以甲基环戊烯为加氢反应的溶剂,采用精馏、加氢和二聚反应相结合的方法,在保证良好的加氢反应效果的前提下,可使简化分离精制的过程,降低能耗。
以下是本发明具体的技术方案。
本发明提供了一种高纯度甲基环戊烯的制备方法,包括:
(1)原料乙烯裂解C9馏分经解聚精馏塔,在常压下馏分中的下双甲基环戊二烯发生解聚,塔顶得到甲基环戊二烯馏分;其中,解聚精馏塔反应条件为塔釜的解聚反应温度160~210℃,塔顶温度70~75℃,回流比1~10;
(2)将步骤(1)得到的甲基环戊二烯和溶剂、氢气混合后连续地通过固定床催化剂床层进行催化加氢反应,催化剂为预硫化处理的改性Ni系催化剂,控制加氢反应条件确保无深度加氢副反应;其中,催化加氢反应条件为溶剂与甲基环戊二烯的重量比为5~10∶1,氢气与甲基环戊二烯的摩尔比为1.0~2.5∶1,反应系统压力0.5~3.0MPa,液时体积空速LHSV为3.0~10.0hr-1;反应温度30~80℃;
(3)将步骤(2)得到的加氢产物进行热二聚反应,以脱除加氢产物中的微量甲基环戊二烯,反应温度80~150℃,反应时间2~12hr,反应压力0.5~3.0MPa;
(4)将步骤(3)得到的物料经甲基环戊烯精制塔进行分离,塔顶得精制甲基环戊烯产品,塔釜物料返回解聚精馏塔;其中,塔顶温度控制在74~80℃,塔釜温度控制在90~110℃,回流比控制为1~10。
进一步的,所述步骤(1)中的解聚精馏塔反应条件为塔釜的解聚反应温度180~190℃,塔顶温度71~73℃,回流比3~6。
进一步的,所述步骤(2)中的预硫化处理的改性Ni系催化剂为钼和钴改性的Ni/Al2O3,镍含量为20~70wt%,载体氧化铝的比表面积为100~300m2/g,孔体积为0.1~0.6ml/g (市售,如武汉科林的W217)。
进一步的,预硫化处理是指在惰性介质下,加入至少一种含硫化合物,含硫化合物的浓度控制在50ppm,在温度为50℃、压力为1.0MPa、停留时间为24hr的条件下进行,制得部分硫化中毒处理的选择加氢催化剂。
进一步的,所述的含硫化合物为二硫化碳、二甲基二硫醚或噻吩。
进一步的,所述步骤(2)中的溶剂与甲基环戊二烯的重量比为6~8∶1,氢气与甲基环戊二烯的摩尔比为1.2~1.8∶1,反应系统压力为1.0~2.5MPa,液时体积空速为4.0~6.0hr-1;反应温度为50~60℃。
进一步的,所述的溶剂为甲基环戊烯。
进一步的,所述步骤(3)中的反应温度为90~100℃,反应时间为6~8hr,反应压力为1.0~1.5MPa。
进一步的,所述步骤(4)中的塔顶温度控制在75~78℃,塔釜温度控制在97~103℃,回流比为2~5。
对于甲基环戊二烯选择性加氢过程,发明人发现,采用部分中毒处理的镍系催化剂可获得较好的加氢选择性。在催化剂硫化处理过程,会形成特定数量的Ni-S中间态,被修饰了Ni晶体,使得催化剂活性位特定数量的减少,在控制一定反应深度的情况下,特定数量的中间态可以完全抑制甲基环戊烯的加氢反应,又不影响甲基环戊二烃加氢,基本保持一种有效的平衡状态。当甲基环戊二烯浓度较低(<1%)时,使得其吸附于不同活性中心的概率降低,很难通过合适的加氢条件来控制甲基环戊烯的进一步加氢,此时可通过成熟的二聚技术除去残留的甲基环戊二烯。此外本发明还采用了与加氢产物甲基环戊烯为反应溶剂,这使得加氢反应体系中减少了一种组分,为加氢产物精制分离的简化打下了基础。
与现有技术相比,本发明在保证良好的加氢反应效果的前提下,采用一个精馏塔即可完成溶剂、加氢产物的分离和精制,分离精制系统得以简化,可减少设备投资和降低运行成本,并获得含量大于99%的高纯度甲基环戊烯。
附图说明
图1为本发明制备高纯度甲基环戊烯的工艺流程示意图。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干调整和改进。这些都属于本发明的保护范围。
以下实施例中所用催化剂可通过市售获得。
【实施例1~10】
实施例1~10的工艺流程见图1,原料W1首先进入反应精馏塔进行解聚反应,塔顶得到甲基环戊二烯(MCPD)的解聚产物W2,反应精馏塔的理论塔板数为30,塔釜定期排放重组分杂质。W2进入固定床反应器加氢,得到加氢产物W3,W3通过二聚反应器聚合及甲基环戊烯精制塔进行分离,最终得到MCPE成品W4。
反应过程如下:
(1)原料乙烯裂解C9馏分(双甲基环戊二烯)经解聚精馏塔,在常压下馏分中的双甲基环戊二烯发生解聚,塔顶得到甲基环戊二烯馏分;
(2)将甲基环戊二烯和溶剂甲基环戊烯、氢气混合后连续地通过固定床催化剂床层进行催化加氢反应,催化剂为预硫化处理的改性Ni系催化剂,控制催化加氢反应条件确保无深度加氢副反应;其中,预硫化处理在惰性介质下,加入至少一种含硫化合物,含硫化合物在物料中的浓度控制在50ppm,在温度为50℃、压力为1.0MPa、停留时间为24hr的条件下进行,制得部分硫化中毒处理的选择加氢催化剂;
(3)将得到的加氢产物进行热二聚反应;
(4)将物料经甲基环戊烯精制塔进行分离,塔顶出得精制甲基环戊烯产品,塔釜物料返回解聚精馏塔。
原料W1为乙烯裂解C9馏分,其主要组成见表1,各实施例中,依次经过反应精馏塔、加氢反应器、二聚反应器和甲基环戊烯精制塔的工艺操作条件分别见表2、表3、表4和表5,反应结束后用气相色谱法进行产物的组成分析,甲基环戊烯产品收率及产物纯度见表6。甲基环戊烯的产品收率定义为:
表1.原料(W1)的主要组份
表2.各实施例的解聚精馏塔内解聚精馏分离反应条件
塔顶温度(℃) | 塔釜温度(℃) | 回流比 | |
实施例1 | 70 | 160 | 1 |
实施例2 | 71.4 | 182 | 3 |
实施例3 | 71.0 | 180 | 3.5 |
实施例4 | 71.6 | 183 | 4.5 |
实施例5 | 72.1 | 186 | 4.0 |
实施例6 | 72 | 185 | 5 |
实施例7 | 72.5 | 188 | 5.5 |
实施例8 | 73 | 190 | 6 |
实施例9 | 74 | 200 | 8 |
实施例10 | 75 | 210 | 10 |
表3.各实施例的固定床反应器内反应条件
表4.各实施例的二聚反应器内反应条件
反应温度(℃) | 反应压力(MPa) | 停留时间(hr) | |
实施例1 | 80 | 0.5 | 12 |
实施例2 | 90 | 1.0 | 10 |
实施例3 | 92 | 1.1 | 8 |
实施例4 | 94 | 1.2 | 7.8 |
实施例5 | 95 | 1.3 | 7.5 |
实施例6 | 96 | 1.3 | 7.2 |
实施例7 | 98 | 1.4 | 7 |
实施例8 | 100 | 1.5 | 6.5 |
实施例9 | 120 | 2.0 | 6 |
实施例10 | 150 | 3.0 | 2 |
表5.各实施例的甲基环戊烯精制塔分离条件
塔顶温度(℃) | 塔釜温度(℃) | 回流比 | |
实施例1 | 95 | 74 | 1 |
实施例2 | 97 | 75 | 2 |
实施例3 | 98 | 75.5 | 3.0 |
实施例4 | 99 | 76 | 2.5 |
实施例5 | 100 | 76.5 | 3.5 |
实施例6 | 101 | 76.8 | 4.5 |
实施例7 | 102 | 77 | 4.0 |
实施例8 | 103 | 77.5 | 8 |
实施例9 | 104 | 78 | 5 |
实施例10 | 105 | 80 | 10 |
表6.各实施例所得甲基环戊烯产品收率及产物纯度
甲基环戊烯收率(%) | 甲基环戊烯纯度(%) | |
实施例1 | 81.5 | 99.0 |
实施例2 | 84.3 | 99.1 |
实施例3 | 85.6 | 99.2 |
实施例4 | 86.0 | 99.3 |
实施例5 | 85.4 | 99.3 |
实施例6 | 84.8 | 99.4 |
实施例7 | 85.2 | 99.3 |
实施例8 | 82.8 | 99.1 |
实施例9 | 83.9 | 99.1 |
实施例10 | 81.7 | 99.0 |
以上已对本发明创造的较佳实施例进行了具体说明,但本发明创造并不限于所述实施例,熟悉本领域的技术人员在不违背本发明创造精神的前提下还可作出种种的等同的变型或替换,这些等同的变型或替换均包含在本申请权利要求所限定的范围内。
Claims (9)
1.一种甲基环戊烯的制备方法,包括:
(1)原料乙烯裂解C9馏分经解聚精馏塔,在常压下馏分中的双甲基环戊二烯发生解聚,塔顶得到甲基环戊二烯馏分;其中,解聚精馏塔反应条件为塔釜的解聚反应温度160~210℃,塔顶温度70~75℃,回流比1~10;
(2)将步骤(1)得到的甲基环戊二烯和溶剂、氢气混合后进行催化加氢反应,催化剂为预硫化处理的改性Ni系催化剂;其中,催化加氢反应条件为溶剂与甲基环戊二烯的重量比为5~10∶1,氢气与甲基环戊二烯的摩尔比为1.0~2.5∶1,反应系统压力0.5~3.0MPa,液时体积空速LHSV为3.0~10.0hr-1;反应温度30~80℃;
(3)将步骤(2)得到的加氢产物进行热二聚反应,反应温度80~150℃,反应时间2~12hr,反应压力0.5~3.0MPa;
(4)将步骤(3)得到的物料经甲基环戊烯精制塔进行分离,塔顶得精制甲基环戊烯,塔釜物料返回解聚精馏塔;其中,塔顶温度控制在74~80℃,塔釜温度控制在90~110℃,回流比控制为1~10。
2.根据权利要求1所述的一种甲基环戊烯的制备方法,其特征在于:所述步骤(1)中的解聚精馏塔反应条件为塔釜的解聚反应温度180~190℃,塔顶温度71~73℃,回流比3~6。
3.根据权利要求1所述的一种甲基环戊烯的制备方法,其特征在于:所述步骤(2)中的预硫化处理的改性Ni系催化剂为钼和钴改性的Ni/Al2O3,镍含量为20~70wt%,载体氧化铝的比表面积为100~300m2/g,孔体积为0.1~0.6ml/g。
4.根据权利要求1或3所述的一种甲基环戊烯的制备方法,其特征在于:所述的预硫化处理是指在惰性介质下,加入至少一种含硫化合物,含硫化合物的浓度控制在50ppm,在温度为50℃、压力为1.0MPa、停留时间为24hr的条件下进行处理,制得部分硫化中毒处理的选择加氢催化剂。
5.根据权利要求4所述的一种甲基环戊烯的制备方法,其特征在于:所述的含硫化合物为二硫化碳、二甲基二硫醚或噻吩。
6.根据权利要求1所述的一种甲基环戊烯的制备方法,其特征在于:所述步骤(2)中的溶剂与甲基环戊二烯的重量比为6~8∶1,氢气与甲基环戊二烯的摩尔比为1.2~1.8∶1,反应系统压力为1.0~2.5MPa,液时体积空速为4.0~6.0hr-1;反应温度为50~60℃。
7.根据权利要求1或4所述的一种甲基环戊烯的制备方法,其特征在于:所述的溶剂为甲基环戊烯。
8.根据权利要求1所述的一种甲基环戊烯的制备方法,其特征在于:所述步骤(3)中的反应温度为90~100℃,反应时间为6~8hr,反应压力为1.0~1.5MPa。
9.根据权利要求1所述的一种甲基环戊烯的制备方法,其特征在于:所述步骤(4)中的塔顶温度控制在75~78℃,塔釜温度控制在97~103℃,回流比为2~5。
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