CN113929558B - Method and device system for purifying and recycling waste alcohol in high-carbon alcohol production - Google Patents
Method and device system for purifying and recycling waste alcohol in high-carbon alcohol production Download PDFInfo
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- CN113929558B CN113929558B CN202111192836.2A CN202111192836A CN113929558B CN 113929558 B CN113929558 B CN 113929558B CN 202111192836 A CN202111192836 A CN 202111192836A CN 113929558 B CN113929558 B CN 113929558B
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 90
- 239000002699 waste material Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000004064 recycling Methods 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- 238000000746 purification Methods 0.000 claims abstract description 129
- 239000007788 liquid Substances 0.000 claims abstract description 84
- 239000000203 mixture Substances 0.000 claims abstract description 62
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 59
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 150000001298 alcohols Chemical class 0.000 claims description 86
- 150000002576 ketones Chemical class 0.000 claims description 48
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 40
- 150000001299 aldehydes Chemical class 0.000 claims description 29
- YLQLIQIAXYRMDL-UHFFFAOYSA-N propylheptyl alcohol Chemical compound CCCCCC(CO)CCC YLQLIQIAXYRMDL-UHFFFAOYSA-N 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 239000005416 organic matter Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 38
- 238000011084 recovery Methods 0.000 description 23
- 239000000047 product Substances 0.000 description 14
- FEFNFOUJRMDJFO-UHFFFAOYSA-N 2-propylheptanal Chemical compound CCCCCC(C=O)CCC FEFNFOUJRMDJFO-UHFFFAOYSA-N 0.000 description 13
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 11
- -1 carbon olefin Chemical class 0.000 description 8
- KRIMXCDMVRMCTC-UHFFFAOYSA-N 2-methylhexan-2-ol Chemical compound CCCCC(C)(C)O KRIMXCDMVRMCTC-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- MTYUOIVEVPTXFX-UHFFFAOYSA-N bis(2-propylheptyl) benzene-1,2-dicarboxylate Chemical compound CCCCCC(CCC)COC(=O)C1=CC=CC=C1C(=O)OCC(CCC)CCCCC MTYUOIVEVPTXFX-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 2
- WNEODWDFDXWOLU-QHCPKHFHSA-N 3-[3-(hydroxymethyl)-4-[1-methyl-5-[[5-[(2s)-2-methyl-4-(oxetan-3-yl)piperazin-1-yl]pyridin-2-yl]amino]-6-oxopyridin-3-yl]pyridin-2-yl]-7,7-dimethyl-1,2,6,8-tetrahydrocyclopenta[3,4]pyrrolo[3,5-b]pyrazin-4-one Chemical compound C([C@@H](N(CC1)C=2C=NC(NC=3C(N(C)C=C(C=3)C=3C(=C(N4C(C5=CC=6CC(C)(C)CC=6N5CC4)=O)N=CC=3)CO)=O)=CC=2)C)N1C1COC1 WNEODWDFDXWOLU-QHCPKHFHSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002085 enols Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000007037 hydroformylation reaction Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- MDVPRIBCAFEROC-BQYQJAHWSA-N (e)-oct-1-en-1-ol Chemical compound CCCCCC\C=C\O MDVPRIBCAFEROC-BQYQJAHWSA-N 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
Abstract
The invention relates to a method and a device system for purifying and recycling waste alcohol in high-carbon alcohol production, wherein the method respectively carries out rectification purification on a first mixture after primary hydrogenation separation and a second mixture after secondary hydrogenation separation under specific conditions, and then carries out hydrogenation on purified liquid obtained by rectification purification to obtain high-carbon alcohol; the device system is only provided with two rectification and purification towers on the basis of an original high-carbon alcohol production system; the invention can realize the purification and recycling of waste alcohol, reduce the discharge of high-carbon alcohol waste liquid, and has the advantages of yield increase and efficiency improvement.
Description
Technical Field
The invention relates to the field of high-carbon alcohol production, in particular to a method and a device system for purifying and recycling waste alcohol in the high-carbon alcohol production.
Background
The high-carbon alcohol refers to monohydric alcohol with carbon number more than or equal to 4, is commonly used for synthesizing fine chemical products such as surfactants, plasticizers, detergents and the like, and is widely applied to the fields of petrochemical industry, mechanical mining, architectural metallurgy, papermaking, food and the like. Among them, 2-propylheptanol (2-PH) is one of the important representatives of higher alcohols. Currently, dioctyl phthalate (DOP) plasticizers are gradually replaced by di (2-propylheptyl) phthalate (DPHP) due to safety problems, and 2-PH, which is a main synthesis raw material of DPHP, has a wide market prospect.
Currently, the main synthesis methods of higher alcohols are oxo, ziegler and normal alkane oxidation, and the preparation raw materials mainly originate from petroleum derivatives. The refinery or coal chemical industry enterprise utilizes low carbon olefin resource, produces aldehydes with increased carbon atoms through hydroformylation reaction, further produces high carbon aldehydes, and then obtains butanol, octanol, 2-PH and other high carbon alcohol products through high carbon aldehyde hydrogenation reaction. In the production of higher alcohols, there is often a large amount of waste alcohol liquor generated, and the problem of treating waste alcohol liquor of 2-PH is relatively serious compared with butanol and octanol. The method is characterized in that the waste alcohol liquid generated in the preparation process of the high-carbon alcohol still contains a large amount of high-carbon alcohol products and active intermediate components thereof, wherein the active intermediate components comprise enol and aldehydes which can be converted into the high-carbon alcohol, and the waste alcohol is large in emission and difficult to directly utilize. At present, waste alcohol is mainly treated in a combustion mode in industry, so that serious resource waste is caused.
CN109503322a discloses a process method for preparing high-carbon alcohol from paraffin, which comprises the steps of heating and stirring solid paraffin and boric acid to obtain an intermediate product, adding sodium hydroxide solution into the intermediate product for dissolution to obtain a high-carbon alcohol crude product, and then obtaining the high-carbon alcohol product through reduced pressure distillation. The preparation conditions of the method are strict, the cost of the preparation raw materials is high, and the method is difficult to popularize in industry.
CN102850181a discloses a process for preparing high-carbon alcohol, which comprises charging hydrogen, fatty acid methyl ester and mixture of C1-C4 alcohol into a fixed bed reactor with hydrogenation catalyst, hydrogenation reacting at 200-320 deg.c and 3.0-7.5MPa, distilling the reaction effluent, and separating the target product high-carbon alcohol. However, the waste liquid obtained after the high-carbon alcohol is separated by the method still contains more products, and the products cannot be recycled.
Therefore, how to recycle the waste alcohol in the high-carbon alcohol production, reduce the production cost and save the resources is a problem to be solved at present.
Disclosure of Invention
Compared with the prior art, the method for purifying and recycling the waste alcohol can realize the re-purification and recycling of the waste alcohol liquid separated after hydrofining, greatly reduce the discharge amount of the waste alcohol liquid, effectively increase the yield of the high-carbon alcohol, and realize industrialized popularization.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the invention provides a method for purifying and recycling waste alcohol in high-carbon alcohol production, which is characterized by comprising the following steps:
(1) Performing first rectification and purification on the first mixture subjected to primary hydrogenation separation at the temperature of between 5 and 7kPa and the temperature of between 120 and 170 ℃ to obtain a first component purification liquid containing organic matters with the carbon number equivalent to that of high-carbon alcohol; the first mixture comprises an organic matter with carbon atoms greater than or equal to that of higher alcohols;
(2) Performing second rectification and purification on the second mixture subjected to secondary hydrogenation separation at the temperature of between 5 and 7kPa and the temperature of between 120 and 160 ℃ to obtain a second component purification liquid containing organic matters with the carbon number equivalent to that of the high-carbon alcohol; the second mixture comprises organic matters with carbon atoms less than or equal to that of higher alcohols;
(3) Hydrofining the first component purification liquid obtained in the step (1) and the second component purification liquid obtained in the step (2) to obtain high-carbon alcohol;
the step (1) and the step (2) have no sequence relation.
In the present invention, the term "higher alcohols" means monohydric alcohols having at least 4 carbon atoms.
In the existing high-carbon alcohol production technology, because impurities contained in high-carbon alcohol production raw materials are complex, side reactions are easy to occur in the hydroformylation reaction process and the like, two hydrofining steps are generally required in a hydrogenation unit of the high-carbon alcohol, and waste alcohol liquid separated after the two hydrofining steps still contains a large amount of high-carbon alcohol and active intermediate components thereof, wherein the active intermediate components comprise enol and aldehydes which can be converted into the high-carbon alcohol, the waste alcohol liquid is difficult to directly utilize, and the waste alcohol liquid is generally treated by adopting a combustion method in industry, so that serious resource waste is caused. In the invention, the first mixture after primary hydrogenation separation and the second mixture after secondary hydrogenation separation are respectively subjected to first rectification purification and second rectification purification, and the first component purification liquid and the second component purification liquid are recovered, wherein the carbon atoms of organic matters contained in the first component purification liquid and the second component purification liquid are equivalent to those of high-carbon alcohol, for example, the organic matters can be high-carbon alcohol or active intermediate components of the high-carbon alcohol. The first component purified liquid and the second component purified liquid are returned to the hydrogenation unit for hydrofining again, and the high-carbon alcohol is prepared. By the method, the recycling of waste alcohol resources is realized, and the yield of high-carbon alcohol can be improved.
In the invention, the first mixture and the second mixture contain higher alcohols and other organic matters with carbon atoms more or less than that of the higher alcohols, and the aim of separating the higher alcohols and the active intermediate components thereof from other organic matters is fulfilled by designing the first rectification purification and the second rectification purification for two times of reduced pressure rectification aiming at the sensitivity of the higher alcohols and the active intermediate components thereof to temperature. According to the invention, on the premise of meeting the separation requirement, the pressure of the first rectification purification and the second rectification purification is controlled to be 5-7kPa (absolute pressure), so that the operation temperature can be reduced, the operation cost is reduced, and the high-carbon alcohol and the active intermediate components thereof can be effectively separated. In the invention, the first rectification and purification operation temperature is controlled to be 120-170 ℃, and the second rectification and purification operation temperature is controlled to be 120-160 ℃, because when the reaction temperature is more than 170 ℃, a part of high-carbon alcohol can be decomposed, and the yield of the high-carbon alcohol is reduced. The operating temperature of the second rectification purification is lower than the operating temperature of the first rectification purification under the same operating pressure. The invention can purify the high-carbon alcohol and the active intermediate component thereof in the first mixture and the second mixture again by playing the synergistic effect of the operating pressure and the temperature, and the recovery rate of the high-carbon alcohol reaches more than 99 percent after the obtained purified liquid is hydrofined again.
In the present invention, the pressure of the first rectification purification is controlled to be 5 to 7kPa, for example, 5kPa, 5.1kPa, 5.2kPa, 5.3kPa, 5.4kPa, 5.5kPa, 5.6kPa, 5.7kPa, 5.8kPa, 5.9kPa, 6kPa, 6.1kPa, 6.2kPa, 6.3kPa, 6.4kPa, 6.5kPa, 6.6kPa, 6.7kPa, 6.8kPa, 6.9kPa or 7kPa may be used, but the present invention is not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
In the present invention, the temperature of the first rectification purification is controlled to 120 to 170 ℃, for example, 120 ℃, 122 ℃, 124 ℃, 126 ℃, 128 ℃, 130 ℃, 132 ℃, 134 ℃, 136 ℃, 138 ℃, 140 ℃, 142 ℃, 144 ℃, 146 ℃,148 ℃,150 ℃, 152 ℃, 154 ℃,156 ℃,158 ℃,160 ℃, 162 ℃, 164 ℃, 166 ℃, 168 ℃, or 170 ℃, but the temperature is not limited to the above-mentioned values, and other values not mentioned in the numerical range are applicable.
In the present invention, the pressure of the second rectification purification is controlled to be 5 to 7kPa, for example, 5kPa, 5.1kPa, 5.2kPa, 5.3kPa, 5.4kPa, 5.5kPa, 5.6kPa, 5.7kPa, 5.8kPa, 5.9kPa, 6kPa, 6.1kPa, 6.2kPa, 6.3kPa, 6.4kPa, 6.5kPa, 6.6kPa, 6.7kPa, 6.8kPa, 6.9kPa or 7kPa may be used, but the present invention is not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
In the present invention, the temperature of the second rectification purification is controlled to be 120 to 160 ℃, for example, 120 ℃, 122 ℃, 124 ℃, 126 ℃, 128 ℃, 130 ℃, 132 ℃, 134 ℃, 136 ℃, 138 ℃, 140 ℃, 142 ℃, 144 ℃, 146 ℃,148 ℃,150 ℃, 152 ℃, 154 ℃,156 ℃,158 ℃, or 160 ℃, but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the first mixture of step (1) comprises any one or a combination of at least two of alcohols, ketones or aldehydes, wherein typical but non-limiting combinations are combinations of alcohols and ketones, combinations of alcohols and aldehydes, combinations of ketones and aldehydes or combinations of alcohols, ketones and aldehydes.
Preferably, the first mixture contains 70% -95% of alcohols, 5% -28% of ketones and 0.4% -2% of aldehydes by mass percent.
Preferably, the first mixture contains alcohols including any one or a combination of at least two of 2-propylheptanol, C13 alcohol, or C15 alcohol, wherein typical but non-limiting combinations are combinations of 2-propylheptanol and 2-propylheptanol, combinations of 2-propylheptanol and C13 alcohol, combinations of 2-propylheptanol and C15 alcohol, or combinations of 2-propylheptanol, C13 alcohol, and C15 alcohol.
Preferably, the mass percentage of higher alcohols in the first mixture is 50-60%, such as 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59% or 60%, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the first mixture contains ketones including any one or a combination of at least two of C10 ketone, C13 ketone or C15 ketone, wherein typical but non-limiting combinations are combinations of C10 ketone and C13 ketone, combinations of C10 ketone and C15 ketone or combinations of C10 ketone, C13 ketone and C15 ketone.
Preferably, the first mixture contains aldehydes including any one or a combination of at least two of 2-propylheptanal, C13 aldehyde or C15 aldehyde, wherein the typical but non-limiting combination is a combination of 2-propylheptanal and C13 aldehyde, a combination of 2-propylheptanal and C15 aldehyde or a combination of 2-propylheptanal, C13 aldehyde and C15 aldehyde.
In the present invention, when the higher alcohol product is 2-pH, the composition of the above-mentioned first mixture is preferably purified for reuse.
Preferably, the mass percentage of the higher alcohols in the first component purification liquid in the step (1) is 71-72%, for example, 71%, 71.1%, 71.2%, 71.3%, 71.4%, 71.5%, 71.6%, 71.7%, 71.8%, 71.9% or 72%, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the mass percentage of the high-carbon alcohol active intermediate component in the first component purification liquid in the step (1) is 27-28%, for example, 27%, 27.1%, 27.2%, 27.3%, 27.4%, 27.5%, 27.6%, 27.7%, 27.8%, 27.9% or 28%, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the mass percentage of the organic matter having carbon atoms greater than that of the higher alcohol in the first component purification liquid in the step (1) is less than 1%, for example, 1%, 0.09%, 0.08%, 0.07%, 0.06%, 0.05%, 0.04%, 0.03%, 0.02% or 0.01%, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the recovery rate of higher alcohols in the first component purification liquid in the step (1) is greater than or equal to 99%, for example, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8% or 99.9%, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
In the present invention, when the higher alcohol product is 2-pH, it is preferable that the composition of the above-mentioned first component purification liquid is purified and reused.
Preferably, the operating pressure of the first rectification purification in step (1) is 5 to 6kPa, and may be, for example, 5kPa, 5.1kPa, 5.2kPa, 5.3kPa, 5.4kPa, 5.5kPa, 5.6kPa, 5.7kPa, 5.8kPa, 5.9kPa or 6kPa, but not limited to the values listed, and other non-listed values within the numerical range are equally applicable.
In the invention, the operation pressure of the first rectification purification is preferably controlled to be 5-6kPa, so that the temperature of the rectification operation can be reduced while the cost of the decompression operation is controlled within an economic and reasonable range.
Preferably, the temperature of the first rectification purification is 130 to 160 ℃, for example 130 ℃, 132 ℃, 134 ℃, 136 ℃, 138 ℃, 140 ℃, 142 ℃, 144 ℃, 146 ℃,148 ℃,150 ℃, 152 ℃, 154 ℃,156 ℃,158 ℃, or 160 ℃, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In the invention, the temperature of the first rectification purification is preferably controlled to be 130-160 ℃, so that the stability of the rectification product can be better ensured, and the reaction such as decomposition and the like caused by over-temperature can be avoided.
Preferably, the condensation temperature of the first rectification purification is 40-60 ℃, for example, 40 ℃,42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃ or 60 ℃, but not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
In the present invention, it is preferable to control the condensing temperature of the first rectification purification to 40 to 60℃in order to reduce the treatment cost while cooling the material.
Preferably, the second mixture of step (2) comprises any one or a combination of at least two of alcohols, ketones, aldehydes or hydrocarbons, wherein typical but non-limiting combinations are combinations of alcohols and ketones, alcohols and aldehydes, alcohols and hydrocarbons, ketones and esters or alcohols, ketones, aldehydes and hydrocarbons.
Preferably, the second mixture contains 90 to 99% by mass of alcohols, 0.5 to 7% by mass of ketones, 0.2 to 0.5% by mass of aldehydes and 0 to 0.1% by mass of hydrocarbons.
Preferably, the second mixture contains alcohols including any one or a combination of at least two of 2-propylheptanol, pentanol, 2, 4-trimethyl-3-pentanol, 2-methyl-2-hexanol, octanol, or 2-propylheptanol, wherein typical but non-limiting combinations are combinations of 2-propylheptanol and pentanol, combinations of 2-propylheptanol and 2, 4-trimethyl-3-pentanol, combinations of 2-propylheptanol and 2-methyl-2-hexanol, or combinations of 2-propylheptanol, pentanol, 2, 4-trimethyl-3-pentanol, 2-methyl-2-hexanol, octanol, and 2-propylheptanol.
Preferably, the mass percentage of the higher alcohol in the second mixture is 20-30%, for example, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% or 30%, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the ketones contained in the second mixture comprise C10 ketones.
Preferably, the aldehydes contained in the second mixture include any one or a combination of two of valeraldehyde and 2-propyl heptanal.
Preferably, the hydrocarbons contained in the second mixture comprise ethane.
In the present invention, when the higher alcohol product is 2-pH, the composition of the above-mentioned second mixture is preferably purified for reuse.
Preferably, the mass percentage of higher alcohols in the second component purification liquid in step (2) is 69-70%, for example 69%, 69.1%, 69.2%, 69.3%, 69.4%, 69.5%, 69.6%, 69.7%, 69.8%, 69.9% or 70%, but not limited to the values listed, and other non-listed values in the range of values are equally applicable.
Preferably, the mass percentage of the high-carbon alcohol active intermediate component in the second component purification liquid in the step (2) is 29-30%, for example, 29%, 29.1%, 29.2%, 29.3%, 29.4%, 29.5%, 29.6%, 29.7%, 29.8%, 29.9% or 30%, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the mass percentage of the organic matter having carbon atoms smaller than that of higher alcohols in the second component purification liquid in the step (2) is less than 0.1%, for example, may be 0.09%, 0.08%, 0.07%, 0.06%, 0.05%, 0.04%, 0.03%, 0.02% or 0.01%, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the recovery rate of higher alcohols in the second component purification liquid in the step (2) is greater than or equal to 99%, for example, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8% or 99.9%, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
In the present invention, when the higher alcohol product is 2-pH, the composition of the above-mentioned second component purification liquid is preferably purified for reuse.
Preferably, the operating pressure of the second rectification purification in step (2) is 5 to 6kPa, and may be, for example, 5kPa, 5.1kPa, 5.2kPa, 5.3kPa, 5.4kPa, 5.5kPa, 5.6kPa, 5.7kPa, 5.8kPa, 5.9kPa or 6kPa, but not limited to the values listed, and other non-listed values within the numerical range are equally applicable.
In the invention, the operation pressure of the second rectification purification is preferably controlled to be 5-6kPa, so that the temperature of the rectification operation can be reduced, and the cost of the decompression operation can be controlled within an economic and reasonable range.
Preferably, the temperature of the second rectification purification is 130-150 ℃, for example 130 ℃, 132 ℃, 134 ℃, 136 ℃, 138 ℃, 140 ℃, 142 ℃, 144 ℃, 146 ℃,148 ℃ or 150 ℃, but the temperature is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
In the invention, the temperature of the second rectification purification is preferably controlled to be 130-150 ℃, so that the stability of the rectification product can be better ensured, and the reaction such as decomposition and the like caused by over-temperature can be avoided.
Preferably, the condensing temperature of the second rectification purification is 40-60 ℃, for example, 40 ℃,42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃ or 60 ℃, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In the present invention, it is preferable to control the condensing temperature of the second rectification purification to 40 to 60℃in order to reduce the treatment cost while cooling the material.
Preferably, the higher alcohols in the step (3) comprise alcohols with carbon number not less than 4.
Preferably, the higher alcohol comprises any one of butanol, octanol or 2-propylheptanol, preferably 2-propylheptanol.
Preferably, the first component purified liquid in step (3) is pressurized before being hydrofinished.
Preferably, the operation pressure of pressurizing the first component purification liquid in the step (3) is 2-3.2MPa, for example, 2MPa, 2.1MPa, 2.2MPa, 2.3MPa, 2.4MPa, 2.5MPa, 2.6MPa, 2.7MPa, 2.8MPa, 2.9MPa, 3MPa, 3.1MPa or 3.2MPa, but not limited to the values listed, and other non-listed values in the range of values are equally applicable, preferably 2.5-3MPa.
Preferably, the second component purified solution of step (3) is pressurized prior to hydrofinishing.
Preferably, the second component purification liquid in step (3) is pressurized at an operating pressure of 2-3.2MPa, for example, 2MPa, 2.1MPa, 2.2MPa, 2.3MPa, 2.4MPa, 2.5MPa, 2.6MPa, 2.7MPa, 2.8MPa, 2.9MPa, 3MPa, 3.1MPa or 3.2MPa, but not limited to the values recited, and other non-recited values within the range of values are equally applicable, preferably 2.5-3MPa.
In the invention, the first component purification liquid and the second component purification liquid can be respectively hydrofined, and can be converged to obtain a recycling stream for hydrofining, when the recycling stream is hydrofined after being converged, the first component purification liquid and the second component purification liquid are required to be pressurized before being converged, and the operation pressure is the same.
In a second aspect, the invention provides a device system for purifying and recycling waste alcohol in high-carbon alcohol production, which is used for completing the method for purifying and recycling waste alcohol in high-carbon alcohol production in the first aspect; the device system comprises a first rectifying tower, a second rectifying tower and a hydrogenation unit, wherein a top discharge port of the first rectifying tower is connected with the hydrogenation unit; and a tower kettle discharge port of the second rectifying tower is connected with a hydrogenation unit.
According to the invention, through the arrangement of the device system of the first rectifying tower, the second rectifying tower and the hydrogenation unit, on one hand, the first rectifying tower and the second rectifying tower are used for purifying the hydrogenation unit again for separating the first mixture and the second mixture, so that the purpose of purifying waste alcohol liquid generated by the hydrogenation unit can be realized, and on the other hand, the top discharge port of the first rectifying tower and the bottom discharge port of the second rectifying tower are connected with the hydrogenation unit, so that the obtained first component purification liquid and second component purification liquid can be returned to the hydrogenation unit again for refining, wherein the high-carbon alcohol active intermediate component can be converted into high-carbon alcohol through hydrogenation again, thereby achieving the effects of recovering waste alcohol resources and improving the yield of the high-carbon alcohol.
Preferably, the hydrogenation unit comprises a first hydrogenation reactor, a third rectifying tower, a second hydrogenation reactor and a fourth rectifying tower which are sequentially connected along the flow direction of the reaction raw materials.
Preferably, a tower bottom discharge port of the third rectifying tower is connected with a feed port of the first rectifying tower.
Preferably, the top outlet of the fourth rectifying tower is connected with the inlet of the second rectifying tower.
Preferably, the top outlet of the first rectifying tower is connected with the feed inlet of the first hydrogenation reactor or the second hydrogenation reactor, preferably with the feed inlet of the first hydrogenation reactor.
Preferably, the tower bottom discharge port of the second rectifying tower is connected with the feed port of the first hydrogenation reactor or the second hydrogenation reactor, preferably with the feed port of the first hydrogenation reactor.
In the invention, the top discharge port of the first rectifying tower and the bottom discharge port of the second rectifying tower are preferably connected with the feed port of the first hydrogenation reactor, so that the first component purification liquid and the second component purification liquid can be subjected to hydrofining twice, the active intermediate components in the first component purification liquid and the second component purification liquid are converted into high-carbon alcohol products to the greatest extent, and the yield of the high-carbon alcohol is improved.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a method for purifying and recycling waste alcohol in high-carbon alcohol production, the recovery rate of the high-carbon alcohol after the obtained first component purification liquid and the second component purification liquid are subjected to hydrofining again can reach more than 99%, the discharge amount of the high-carbon alcohol waste liquid is greatly reduced, and the yield of the high-carbon alcohol is improved.
(2) The invention provides a device system for purifying and recycling waste alcohol in high-carbon alcohol production, which has a simple structure, can fully recycle the high-carbon alcohol, realizes yield and efficiency increase, and can be industrially popularized.
Drawings
FIG. 1 is a process flow diagram of a method for purifying and recycling waste alcohol in the production of higher alcohols in example 1 of the present invention;
FIG. 2 is a process flow diagram of a method for purifying and recycling waste alcohol in the production of higher alcohols in example 2 of the present invention.
Wherein, 1-a first hydrogenation reactor; 2-a third rectifying tower; 3-a second hydrogenation reactor; 4-a fourth rectifying tower; 5-a second rectifying tower; 6-a first rectifying tower.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a device system for purifying and recycling waste alcohol in high-carbon alcohol production, which is shown in fig. 1, and comprises a first rectifying tower 6, a second rectifying tower 5 and a hydrogenation unit, wherein a top discharge port of the first rectifying tower 6 is connected with the hydrogenation unit; a tower kettle discharge port of the second rectifying tower 5 is connected with a hydrogenation unit; the hydrogenation unit comprises a first hydrogenation reactor 1, a third rectifying tower 2, a second hydrogenation reactor 3 and a fourth rectifying tower 4 which are sequentially connected along the flow direction of the reaction raw materials; the discharge port of the tower kettle of the third rectifying tower 2 is connected with the feed port of the first rectifying tower 6; the top discharge port of the fourth rectifying tower 4 is connected with the feed port of the second rectifying tower 5; the top discharge port of the first rectifying tower 6 and the bottom discharge port of the second rectifying tower 5 are connected with the first hydrogenation reactor 1.
The embodiment also provides a method for purifying and recycling waste alcohol in high-carbon alcohol production by using the device system for purifying and recycling waste alcohol in high-carbon alcohol production, which comprises the following steps:
(1) Performing first rectification purification on a first mixture subjected to primary hydrogenation separation of 6000kg/h of C10 enal at 5.2kPa (absolute pressure) and 158 ℃ to obtain a first component purification liquid containing organic matters with the carbon number equivalent to that of 2-PH at the temperature of a tower top condenser of 60 ℃, wherein the first mixture contains 80% of alcohols (comprising 60% of 2-PH, 11.4% of 2-propylheptanol, 5% of C13 alcohols and 3.6% of C15 alcohols), 0.4% of 2-propylheptanal and 19.6% of ketones (comprising 8% of C10 ketones, 3% of C13 ketones and 8.6% of C15 ketones) by mass percentage, and the mass percentage of 2-PH is 60%;
(2) Subjecting the second mixture after the secondary hydrogenation separation to a second rectification purification at a temperature of 5.5kPa (absolute pressure) and a temperature of 150 ℃ at a tower top condenser of 60 ℃ to obtain a second component purification liquid containing an organic matter having a carbon number equivalent to that of 2-PH, wherein the second mixture contains 93% of alcohols (including 25% of 2-PH, 14.3% of amyl alcohol, 12.3% of 2, 4-trimethyl-3-amyl alcohol, 17.9% of 2-methyl-2-hexanol, 13.5% of octanol and 10% of 2-propylheptanol), 6.5% of C10 ketones and 0.4% of aldehydes (including 0.1% of valeraldehyde and 0.3% of 2-propylheptanal) and 0.1% of ethane by mass percent, and wherein the 2-PH mass percent is 25%;
(3) The first component purification liquid and the second component purification liquid are respectively pressurized to 2.9MPa and then are converged to obtain a recycling material flow for hydrofining to obtain 2-PH.
Example 2
The embodiment provides a device system for purifying and recycling waste alcohol in high-carbon alcohol production, which comprises a first rectifying tower 6, a second rectifying tower 5 and a hydrogenation unit, wherein a discharge port at the top of the first rectifying tower 6 is connected with the hydrogenation unit as shown in fig. 2; a tower kettle discharge port of the second rectifying tower 5 is connected with a hydrogenation unit; the hydrogenation unit comprises a first hydrogenation reactor 1, a third rectifying tower 2, a second hydrogenation reactor 3 and a fourth rectifying tower 4 which are sequentially connected along the flow direction of the reaction raw materials; the discharge port of the tower kettle of the third rectifying tower 2 is connected with the feed port of the first rectifying tower 6; the top discharge port of the fourth rectifying tower 4 is connected with the feed port of the second rectifying tower 5; the top discharge port of the first rectifying tower 6 and the bottom discharge port of the second rectifying tower 5 are connected with the second hydrogenation reactor 3.
The embodiment also provides a method for purifying and recycling waste alcohol in high-carbon alcohol production by using the device system for purifying and recycling waste alcohol in high-carbon alcohol production, which comprises the following steps:
(1) 7000kg/h of a first mixture after primary hydrogenation of C10 enal is subjected to first rectification purification at 5.1kPa (absolute pressure) and 156 ℃ to obtain a first component purification liquid containing organic matters with the carbon number equivalent to that of 2-PH, wherein the first mixture contains 77% of alcohols (comprising 58% of 2-PH, 10.4% of 2-propylheptanol, 5% of C13 alcohols and 3.6% of C15 alcohols), 1.1% of 2-propylheptanal and 21.9% of ketones (comprising 9% of C10 ketones, 4% of C13 ketones and 8.9% of C15 ketones) by mass percentage, and the mass percentage of 2-PH is 58%;
(2) The second mixture after the secondary hydrogenation separation is subjected to second rectification at a temperature of 5.4kPa (absolute pressure) and 148 ℃ to obtain a second component purification liquid containing organic matters with the carbon number equivalent to that of 2-PH, wherein the second mixture contains 94 percent of alcohols (comprising 23 percent of 2-PH, 14.1 percent of amyl alcohol, 13.6 percent of 2, 4-trimethyl-3-amyl alcohol, 17.8 percent of 2-methyl-2-hexanol, 14.5 percent of octanol and 11 percent of 2-propyl heptanol), 5.5 percent of C10 ketone, 0.45 percent of aldehydes (comprising 0.1 percent of valeraldehyde and 0.3 percent of 2-propyl heptanal) and 0.05 percent of ethane according to the mass percent, and the mass percent of 2-PH is 23 percent;
(3) The first component purification liquid and the second component purification liquid are respectively pressurized to 3.0MPa and then are converged to obtain a recycling material flow for hydrofining to obtain 2-PH.
Example 3
The embodiment provides a method for purifying and recycling waste alcohol in high-carbon alcohol production by using the device system provided in the embodiment 1, wherein the method comprises the following steps:
(1) Performing first rectification purification on a first mixture subjected to primary hydrogenation separation of 6000kg/h of C10 enal at a temperature of 7kPa (absolute pressure) and a temperature of 170 ℃ to obtain a first component purification liquid containing organic matters with carbon atoms equivalent to 2-PH carbon atoms, wherein the first mixture contains 72% of alcohols (comprising 50% of 2-PH, 11.4% of 2-propylheptanol, 6% of C13 alcohols and 4.6% of C15 alcohols), 2% of 2-propylheptanal and 26% of ketones (comprising 11% of C10 ketones, 6% of C13 ketones and 9% of C15 ketones) by mass percentage, and the mass percentage of 2-PH is 50%;
(2) Subjecting the second mixture after the secondary hydrogenation separation to a second rectification purification at a temperature of 160 ℃ at a temperature of 60 ℃ to obtain a second component purification liquid containing an organic matter with a carbon number equivalent to that of 2-PH, wherein the second mixture contains 93% of alcohols (comprising 20% of 2-PH, 15.1% of amyl alcohol, 14.6% of 2, 4-trimethyl-3-amyl alcohol, 17.8% of 2-methyl-2-hexanol, 14.5% of octanol and 11% of 2-propyl heptanol), 6.5% of C10 ketones, 0.45% of aldehydes (comprising 0.1% of valeraldehyde and 0.3% of 2-propyl heptanal) and 0.05% of ethane by mass percent, wherein the 2-PH content is 20%;
(3) The first component purification liquid and the second component purification liquid are respectively pressurized to 2MPa and then are converged to obtain a recycling material flow for hydrofining to obtain 2-PH.
Example 4
The embodiment provides a method for purifying and recycling waste alcohol in high-carbon alcohol production by using the device system provided in the embodiment 1, wherein the method comprises the following steps:
(1) Performing first rectification purification on a first mixture subjected to primary hydrogenation separation of 6000kg/h of C10 enal at a temperature of 161 ℃ at a temperature of 60 ℃ to obtain a first component purification liquid containing organic matters with carbon atoms equivalent to 2-PH carbon atoms, wherein the first mixture contains 77% of alcohols (comprising 55% of 2-PH, 11.4% of 2-propylheptanol, 6% of C13 alcohol and 4.6% of C15 alcohol), 2% of 2-propylheptanal and 21% of ketones (comprising 11% of C10 ketone, 4% of C13 ketone and 6% of C15 ketone) by mass percent, wherein the mass percent of 2-PH is 55%;
(2) Subjecting the second mixture after the secondary hydrogenation separation to a second rectification purification at a temperature of 156 ℃ under 6kPa (absolute pressure), wherein the temperature of the overhead condenser is 60 ℃ to obtain a second component purification liquid containing an organic matter having a carbon number equivalent to that of 2-PH, wherein the second mixture contains 96% by mass of alcohols (including 25% of 2-PH, 13.1% of pentanol, 14.6% of 2, 4-trimethyl-3-pentanol, 16.8% of 2-methyl-2-hexanol, 14.5% of octanol and 12% of 2-propylheptanol), 3.5% of C10 ketones, 0.45% of aldehydes (including 0.1% of valeraldehyde and 0.3% of 2-propylheptanal) and 0.05% of ethane, wherein the 2-PH mass percentage is 25%;
(3) The first component purification liquid and the second component purification liquid are respectively pressurized to 2.6MPa and then are converged to obtain a recycling material flow for hydrofining to obtain 2-PH.
Example 5
The embodiment provides a method for purifying and recycling waste alcohol in high-carbon alcohol production by using the device system provided in the embodiment 1, wherein the method comprises the following steps:
(1) Subjecting a first mixture after primary hydrogenation separation of 5000kg/h of C8 olefine aldehyde to first rectification purification at a temperature of 6kPa (absolute pressure) and 160 ℃ to obtain a first component purification liquid containing organic matters with the carbon number equivalent to that of octanol, wherein the first mixture contains 68% of alcohols (comprising 50% of octanol, 6% of C12 alcohols, 12% of C16 alcohols and the like), 22% of aldehydes (comprising 9% of octanal and 12% of C12 aldehydes) and 10% of ketones (comprising 8% of C8 ketones and 2% of C12 ketones) by mass percent, and the octanol mass percent is 50%;
(2) The second mixture after the secondary hydrogenation separation is subjected to second rectification purification at the temperature of 6kPa (absolute pressure) and 150 ℃, the temperature of a tower top condenser is 60 ℃ to obtain a second component purification liquid containing organic matters with the carbon number equal to that of octanol, wherein the second mixture contains 44% of alcohols (comprising 22% of octanol, 12% of butanol and 10% of octenol), 42% of aldehydes (comprising 23% of butyraldehyde and 19% of octanal), 14% of ketones (comprising 9% of butanone and 5% of octanone) by mass percent, and the octanol mass percent is 22%;
(3) And respectively pressurizing the first component purification liquid and the second component purification liquid to 2.5MPa, merging to obtain a recycling stream, and hydrofining to obtain octanol.
The mass percentage of octanol in the first component purification liquid obtained in this example was 60%, the mass percentage of the active intermediate component was 39.5%, the mass percentage of octanol in the second component purification liquid was 46.3%, the mass percentage of the active intermediate component was 53%, and the recovery rate of octanol obtained in this example was 99%.
Comparative example 1
This comparative example provides a method for purifying and recycling waste alcohol in the production of higher alcohols, which is compared with example 1 only in that the pressure of the first rectification purification is 4kPa.
Comparative example 2
This comparative example provides a method for purifying and recycling waste alcohol in the production of higher alcohols, which is compared with example 1 only in that the pressure of the first rectification purification is 8kPa.
Comparative example 3
This comparative example provides a method for purifying and recycling waste alcohol in the production of higher alcohols, which is compared with example 1 only in that the temperature of the first rectification purification is 110 ℃.
Comparative example 4
This comparative example provides a method for purifying and recycling waste alcohol in the production of higher alcohols, which is compared with example 1 only in that the temperature of the first rectification purification is 180 ℃.
Comparative example 5
This comparative example provides a method for purifying and recycling waste alcohol in the production of higher alcohols, which is compared with example 1 only in that the pressure of the second rectification purification is 4kPa.
Comparative example 6
This comparative example provides a method for purifying and recycling waste alcohol in the production of higher alcohols, which is only characterized in that the pressure of the second rectification purification is 8kPa compared with example 1.
Comparative example 7
This comparative example provides a method for purifying and recycling waste alcohol in the production of higher alcohols, which is compared with example 1 only in that the temperature of the second rectification purification is 110 ℃.
Comparative example 8
This comparative example provides a method for purifying and recycling waste alcohol in the production of higher alcohols, which is compared with example 1 only in that the temperature of the second rectification purification is 170 ℃.
The mass percentages of 2-PH in the first component purified liquid and the second component purified liquid obtained in examples 1 to 4 and comparative examples 1 to 8 were measured by Shimadzu gas chromatography (GC Smart, GC-2018), and the results are shown in Table 1.
The mass percentages of the 2-PH-active intermediate components in the first component purified liquid and the second component purified liquid obtained in examples 1 to 4 and comparative examples 1 to 8 were measured by Shimadzu gas chromatography (GC Smart, GC-2018), and the results are shown in Table 1.
The purification and reuse processes of the waste alcohols in examples 1 to 4 and comparative examples 1 to 8 were simulated using Aspen Plus, and recovery rates of 2-PH are shown in Table 1.
TABLE 1
It can be seen from the combination of example 1 and comparative examples 1 to 2 that the pressure of the first rectification purification was 5.2kPa, the recovery rate of the higher alcohols in example 1 was 99.2% compared to 4kPa and 8kPa in comparative examples 1 and 2, respectively, whereas the recovery rate of the higher alcohols in comparative example 1 was only 94.8%, and the operation cost was high; the recovery rate of the higher alcohols in comparative example 2 was only 89.0%, thus showing that the present invention can improve the recovery rate of the higher alcohols and reduce the operation cost by controlling the pressure of the first rectification purification to 5 to 7 kPa.
It can be seen from the combination of example 1 and comparative examples 3 to 4 that the temperature of the first rectification purification was 156 c, the recovery rate of the higher alcohols in example 1 was 99.2% and the recovery rate of the higher alcohols in comparative example 3 was only 83.8%, the recovery rate of the higher alcohols in comparative example 4 was only 90.1%, and a part of the higher alcohols were easily decomposed, compared to 110 c and 180 c in comparative example 3 and comparative example 4, respectively, thereby showing that the present invention can improve the recovery rate of the higher alcohols and avoid the thermal decomposition of the higher alcohols by controlling the temperature of the first rectification purification to 120 to 170 c.
It can be seen from the combination of example 1 and comparative examples 5 to 6 that the pressure of the second rectification purification was 5.5kPa, the recovery rate of the higher alcohols in example 1 was 99.2% and the recovery rate of the higher alcohols in comparative example 5 was only 97.9% as compared to 4kPa and 8kPa in comparative example 5 and comparative example 6, respectively, and the operation cost was high; the recovery rate of the higher alcohols in comparative example 6 was only 96.8%, thus showing that the present invention can improve the recovery rate of the higher alcohols and reduce the operation cost by controlling the pressure of the second rectification purification to 5 to 7 kPa.
It can be seen from the combination of example 1 and comparative examples 7 to 8 that the temperature of the second rectification purification was 150 c, the recovery rate of the higher alcohols in example 1 was 99.2% and the recovery rate of the higher alcohols in comparative example 7 was only 90.7%, the recovery rate of the higher alcohols in comparative example 8 was only 95.5%, and a part of the higher alcohols were easily decomposed, compared to 110 c and 170 c in comparative example 7 and comparative example 8, respectively, thereby showing that the present invention can improve the recovery rate of the higher alcohols and avoid the thermal decomposition of the higher alcohols by controlling the temperature of the second rectification purification to 120 to 160 c.
In summary, the method and the device system for purifying and recycling the waste alcohol in the production of the high-carbon alcohol can improve the recovery rate of the high-carbon alcohol to more than 99%, reduce the emission of waste alcohol liquid, improve the yield of the high-carbon alcohol and realize the yield and efficiency increase.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (9)
1. The method for purifying and recycling waste alcohol in the production of high-carbon alcohol is characterized by comprising the following steps of:
(1) Performing first rectification and purification on the first mixture subjected to primary hydrogenation separation at the temperature of between 5 and 7kPa and the temperature of between 120 and 170 ℃ to obtain a first component purification liquid containing organic matters with the carbon number equivalent to that of high-carbon alcohol; the first mixture comprises an organic matter with carbon atoms greater than or equal to that of higher alcohols;
the condensation temperature of the first rectification purification is 40-60 ℃;
the first mixture contains 70-95% of alcohols, 5-28% of ketones and 0.4-2% of aldehydes by mass percent; the mass percentage of the high-carbon alcohol in the first mixture is 50-60%;
(2) Performing second rectification and purification on the second mixture subjected to secondary hydrogenation separation at the temperature of between 5 and 7kPa and the temperature of between 120 and 160 ℃ to obtain a second component purification liquid containing organic matters with the carbon number equivalent to that of the high-carbon alcohol; the second mixture comprises organic matters with carbon atoms less than or equal to that of higher alcohols;
the condensing temperature of the second rectification purification is 40-60 ℃;
the second mixture contains 90-99% of alcohols, 0.5-7% of ketones, 0.2-0.5% of aldehydes and 0-0.1% of hydrocarbons by mass percent;
the mass percentage of the high-carbon alcohol in the second mixture is 20-30%;
(3) Hydrofining the first component purification liquid obtained in the step (1) and the second component purification liquid obtained in the step (2) to obtain high-carbon alcohol;
pressurizing the first component purification liquid before hydrofining;
the operation pressure of pressurizing the first component purification liquid is 2-3.2MPa;
pressurizing the second component purification liquid before hydrofining;
the operation pressure of pressurizing the second component purification liquid is 2-3.2MPa;
step (1) and step (2) have no precedence relationship
The higher alcohols include alcohols having at least 4 carbon atoms.
2. The process of claim 1, wherein the operating pressure of the first rectification purification of step (1) is from 5 to 6kPa.
3. The method of claim 1, wherein the temperature of the first rectification purification is 130-160 ℃.
4. The process of claim 1, wherein the second rectification purification of step (2) is operated at a pressure of from 5 to 6kPa.
5. The method of claim 1, wherein the temperature of the second rectification purification is 130-150 ℃.
6. The method of claim 1, wherein the higher alcohol comprises any one of butanol, octanol, or 2-propylheptanol.
7. The method of claim 6 wherein the higher alcohol is 2-propylheptanol.
8. The method of claim 1, wherein the first component purification liquid of step (3) is pressurized at an operating pressure of 2.5 to 3MPa.
9. The method of claim 1, wherein the second component purification liquid of step (3) is pressurized at an operating pressure of 2.5 to 3MPa.
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| CN106187694A (en) * | 2015-04-29 | 2016-12-07 | 中国石油化工股份有限公司 | From butanol and octanol waste liquid, the process for purification of butanol and capryl alcohol is reclaimed by cracking and hydrogenation reaction |
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