CN113929558A - 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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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 194
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000002699 waste material Substances 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- 238000004064 recycling Methods 0.000 title claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 77
- 238000000746 purification Methods 0.000 claims abstract description 77
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 68
- 239000000203 mixture Substances 0.000 claims abstract description 55
- 238000000926 separation method Methods 0.000 claims abstract description 19
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 40
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- YLQLIQIAXYRMDL-UHFFFAOYSA-N propylheptyl alcohol Chemical compound CCCCCC(CO)CCC YLQLIQIAXYRMDL-UHFFFAOYSA-N 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 239000005416 organic matter Substances 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 description 46
- 230000000052 comparative effect Effects 0.000 description 40
- 150000001298 alcohols Chemical class 0.000 description 33
- 150000001299 aldehydes Chemical class 0.000 description 29
- 238000011084 recovery Methods 0.000 description 25
- -1 60% of 2-PH Chemical class 0.000 description 16
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- FEFNFOUJRMDJFO-UHFFFAOYSA-N 2-propylheptanal Chemical compound CCCCCC(C=O)CCC FEFNFOUJRMDJFO-UHFFFAOYSA-N 0.000 description 11
- ZVIXJWDKOACIQD-UHFFFAOYSA-N 2-propylhept-1-en-1-ol Chemical compound CCCCCC(=CO)CCC ZVIXJWDKOACIQD-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- KRIMXCDMVRMCTC-UHFFFAOYSA-N 2-methylhexan-2-ol Chemical compound CCCCC(C)(C)O KRIMXCDMVRMCTC-UHFFFAOYSA-N 0.000 description 7
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 6
- AXINNNJHLJWMTC-UHFFFAOYSA-N 2,2,4-trimethylpentan-3-ol Chemical compound CC(C)C(O)C(C)(C)C AXINNNJHLJWMTC-UHFFFAOYSA-N 0.000 description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 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
- 238000004821 distillation Methods 0.000 description 3
- 238000007037 hydroformylation reaction Methods 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
- 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
- 150000001721 carbon Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002085 enols Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000012535 impurity Substances 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
- 238000007086 side reaction Methods 0.000 description 2
- 238000001308 synthesis method 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
- GADNZGQWPNTMCH-UHFFFAOYSA-N 2-propylhept-2-enal Chemical compound CCCCC=C(C=O)CCC GADNZGQWPNTMCH-UHFFFAOYSA-N 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- 230000009286 beneficial effect 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
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- HFJRKMMYBMWEAD-UHFFFAOYSA-N dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 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
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 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
- 239000002440 industrial waste Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 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
- 230000002194 synthesizing effect Effects 0.000 description 1
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 comprises the steps of respectively carrying out rectification purification on a first mixture subjected to primary hydrogenation separation and a second mixture subjected to secondary hydrogenation separation under specific conditions, and hydrogenating a purified liquid obtained by rectification purification again to obtain high-carbon alcohol; the device system is only provided with two rectifying and purifying towers on the basis of the original high-carbon alcohol production system; the invention can realize the purification and recycling of the waste alcohol, reduce the discharge of high-carbon alcohol waste liquid and has the advantages of yield increase and efficiency increase.
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 high-carbon alcohol production.
Background
The higher alcohol refers to monohydric alcohol with carbon atom 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, building metallurgy, papermaking, food and the like. Among them, 2-propylheptanol (2-PH) is one of the important representatives of higher alcohols. At present, dioctyl phthalate (DOP) plasticizer is gradually replaced by di (2-propyl heptyl) phthalate (DPHP) due to safety problem, and 2-PH as a main synthetic raw material of DPHP has wide market prospect.
The main synthesis methods of the high-carbon alcohol at present are a oxo synthesis method, a Ziegler method and an n-alkane oxidation method, and the preparation raw materials of the high-carbon alcohol mainly come from petroleum derivatives. The method comprises the steps of utilizing low-carbon olefin resources by refineries or coal chemical enterprises, producing aldehydes with increased carbon atoms through hydroformylation reaction, further producing high-carbon aldehydes, and then obtaining high-carbon alcohol products such as butanol, octanol and 2-PH through hydrogenation reaction of the high-carbon aldehydes. In the production of higher alcohols, a large amount of waste alcohol liquid is often produced, and the problem of waste alcohol liquid treatment at 2-PH is relatively serious compared to butanol and octanol. The problems that impurities contained in the raw materials for preparing the higher alcohols are complex, side reactions occur in the hydroformylation reaction process and the like are solved, and the waste alcohol liquid generated in the preparation process of the higher alcohols still contains a large amount of higher alcohol products and active intermediate components thereof, wherein the active intermediate components comprise enol and aldehydes which can be converted into the higher alcohols, and the waste alcohols are large in emission and difficult to directly utilize. At present, the industrial waste alcohol is mainly treated by a combustion mode, which causes serious resource waste.
CN109503322A discloses a process for preparing high carbon alcohol from paraffin, which comprises heating and stirring solid paraffin and boric acid to obtain intermediate product, adding sodium hydroxide solution into the intermediate product to dissolve, to obtain high carbon alcohol crude product, and distilling under reduced pressure to obtain high carbon alcohol product. The method has strict preparation conditions and high cost of preparation raw materials, and is difficult to industrially popularize.
CN102850181A discloses a preparation method of high-carbon alcohol, which comprises the steps of introducing a mixture of hydrogen, fatty acid methyl ester and C1-C4 alcohol into a fixed bed reactor filled with a hydrogenation catalyst, carrying out hydrogenation reaction at the temperature of 200-320 ℃ and the pressure of 3.0-7.5MPa, and separating the target product high-carbon alcohol after distilling the reaction effluent. 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 production of the high-carbon alcohol, reduce the production cost and save resources is a problem which needs to be solved at present.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a method and an apparatus system for purifying and recycling waste alcohol in high-carbon alcohol production, wherein compared with the prior art, the method for purifying and recycling waste alcohol provided by the present invention can realize re-purification and recycling of waste alcohol liquid separated after hydrorefining, greatly reduce the discharge amount of waste alcohol liquid, and effectively increase the yield of high-carbon alcohol.
In order to achieve the purpose, 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) carrying out first rectification and purification on the first mixture subjected to primary hydrogenation separation at the temperature of between 5 and 7kPa and between 120 and 170 ℃ to obtain a first component purification solution containing organic matters with carbon atoms equivalent to those of the high-carbon alcohol; the first mixture comprises organic matter with the carbon number being more than or equal to that of the higher alcohol;
(2) performing second rectification and purification on the second mixture after the secondary hydrogenation separation at the temperature of between 5 and 7kPa and between 120 and 160 ℃ to obtain a second component purification solution containing organic matters with the carbon number equivalent to that of the high-carbon alcohol; the second mixture comprises organic matter with the carbon number less than or equal to that of the high-carbon alcohol;
(3) hydrorefining the first component purified liquid obtained in the step (1) and the second component purified liquid obtained in the step (2) to obtain high-carbon alcohol;
the step (1) and the step (2) have no precedence relationship.
In the present invention, the "higher alcohol" refers to a monohydric alcohol having 4 or more carbon atoms.
In the existing high-carbon alcohol production technology, due to the problems that impurities contained in a high-carbon alcohol production raw material are complex, side reactions are easy to occur in a hydroformylation reaction process and the like, a hydrogenation unit of the high-carbon alcohol generally needs to be subjected to twice hydrofining, and a waste alcohol solution separated after twice hydrofining 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 solution is difficult to directly utilize, and the industrial treatment is generally carried out by adopting a combustion method, so that serious resource waste is caused. In the invention, the first mixture after the primary hydrogenation separation and the second mixture after the secondary hydrogenation separation are respectively subjected to first rectification purification and second rectification purification, and a first component purified liquid and a second component purified liquid are obtained by recovery, wherein the carbon atom number of organic matters contained in the first component purified liquid and the second component purified liquid is equivalent to that of a higher alcohol, such as the higher alcohol or an active intermediate component of the higher alcohol. The obtained first component purified liquid and second component purified liquid are returned to the hydrogenation unit for hydrofining again, and the high carbon alcohol is prepared. By the method, the waste alcohol resource is recycled, and the yield of the high-carbon alcohol can be improved.
According to the invention, aiming at the sensitivity of the high-carbon alcohol and the active intermediate components thereof to temperature, the first rectification and purification and the second rectification and purification are designed for twice reduced pressure rectification, so that the purpose of separating the high-carbon alcohol and the active intermediate components thereof from other organic matters is achieved. In the invention, on the premise of meeting the separation requirement, the pressure of the first rectification purification and the pressure of the second rectification purification are controlled to be 5-7kPa (the pressure is absolute pressure), so that the operation temperature can be reduced, the operation cost can be reduced, and the high-carbon alcohol and the active intermediate component thereof can be effectively separated. In the invention, the first distillation and purification operation temperature is controlled to be 120-170 ℃, and the second distillation and purification operation temperature is controlled to be 120-160 ℃, because when the reaction temperature is higher 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 at the same operating pressure. The method can purify the high-carbon alcohol and the active intermediate components thereof in the first mixture and the second mixture again by exerting the synergistic effect of the operating pressure and the operating temperature, and the recovery rate of the obtained high-carbon alcohol can reach more than 99 percent after the obtained purification liquid is subjected to hydrofining again.
In the present invention, the pressure for the first rectification purification is controlled to be 5 to 7kPa, and may be, 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, but not limited to the values listed, and other values not listed in the numerical ranges are also applicable.
In the present invention, the temperature for the first rectification and purification is controlled to be 120-170 ℃, 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 present invention is not limited to the recited values, and other values not recited in the numerical range are also applicable.
In the present invention, the pressure for the second rectification purification is controlled to be 5 to 7kPa, and may be, 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, but not limited to the values listed, and other values not listed in the numerical ranges are also applicable.
In the present invention, the temperature for the second distillation and purification is controlled to be 120-160 ℃, and 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 recited values, and other values not recited in the numerical range are also applicable.
Preferably, the first mixture in step (1) includes any one or a combination of at least two of alcohols, ketones or aldehydes, wherein typical but non-limiting combinations are a combination of alcohols and ketones, a combination of alcohols and aldehydes, a combination of ketones and aldehydes or a combination of alcohols, ketones and aldehydes.
Preferably, the first mixture comprises 70-95% of alcohols, 5-28% of ketones and 0.4-2% of aldehydes by mass percentage.
Preferably, the alcohols contained in the first mixture include any one of, or a combination of at least two of, 2-propyl heptanol, C13 alcohol, or C15 alcohol, with typical but non-limiting combinations being a combination of 2-propyl heptanol and 2-propyl heptanol, a combination of 2-propyl heptanol and C13 alcohol, a combination of 2-propyl heptanol and C15 alcohol, or a combination of 2-propyl heptanol, C13 alcohol, and C15 alcohol.
Preferably, the higher alcohol is present in the first mixture in an amount of 50-60% by mass, for example 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59% or 60% by mass, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the ketones contained in the first mixture include any one or a combination of at least two of C10 ketones, C13 ketones, or C15 ketones, with typical but non-limiting combinations being a combination of C10 ketones and C13 ketones, a combination of C10 ketones and C15 ketones, or a combination of C10 ketones, C13 ketones, and C15 ketones.
Preferably, the aldehydes contained in the first mixture include any one of 2-propylheptanal, C13 aldehyde, or C15 aldehyde, or a combination of at least two thereof, with typical but non-limiting combinations being 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 to PH, the composition of the first mixture is preferably purified for reuse.
Preferably, the mass percentage of the higher alcohol in the first component purified liquid in 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 values not recited in the range of the values are also applicable.
Preferably, the mass percentage of the higher alcohol active intermediate component in the first component purification solution in 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 values in the range of the recited values are also applicable.
Preferably, the mass percentage of the organic substance having a carbon number greater than that of the higher alcohol in the first component purified liquid in 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 values not recited in the range of values are also applicable.
Preferably, the recovery rate of higher alcohols in the first component purified liquid in step (1) is 99% or more, and may be, for example, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8% or 99.9%, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
In the present invention, when the higher alcohol product is 2-PH, the composition of the first component purification solution is preferably purified for reuse.
Preferably, the first rectification purification of step (1) is operated at a pressure of 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 is not limited to the recited values, and other values not recited in 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, and the cost of the pressure reduction operation can be controlled within an economic and reasonable range.
Preferably, the temperature of the first rectification purification is 130-160 ℃, 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 unrecited values in the range of values are also applicable.
In the invention, the temperature of the first rectification and purification is preferably controlled to be 130-160 ℃, so that the stability of the rectification product can be better ensured, and the reactions such as decomposition and the like due to overtemperature can be avoided.
Preferably, the condensation temperature of the first rectification purification is 40 to 60 ℃, for example 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃ or 60 ℃, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
In the present invention, it is preferable to control the condensation 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 in step (2) includes any one or a combination of at least two of alcohols, ketones, aldehydes or hydrocarbons, wherein typical but non-limiting combinations are a combination of alcohols and ketones, a combination of alcohols and aldehydes, a combination of alcohols and hydrocarbons, a combination of ketones and esters or a combination of alcohols, ketones, aldehydes and hydrocarbons.
Preferably, the second mixture comprises 90-99% of alcohols, 0.5-7% of ketones, 0.2-0.5% of aldehydes and 0-0.1% of hydrocarbons by weight percentage.
Preferably, the second mixture contains alcohols including any one of 2-propyl heptanol, pentanol, 2, 4-trimethyl-3-pentanol, 2-methyl-2-hexanol, octanol, or 2-propyl heptanol, or a combination of at least two thereof, wherein typical but non-limiting combinations are a combination of 2-propyl heptanol and pentanol, a combination of 2-propyl heptanol and 2,2, 4-trimethyl-3-pentanol, a combination of 2-propyl heptanol and 2-methyl-2-hexanol, or a combination of 2-propyl heptanol, pentanol, 2, 4-trimethyl-3-pentanol, 2-methyl-2-hexanol, octanol, and 2-propyl heptanol.
Preferably, the higher alcohol is present in the second mixture in an amount of 20-30% by weight, for example 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% or 30% by weight, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the ketones contained in the second mixture include C10 ketones.
Preferably, the second mixture comprises aldehydes comprising either or a combination of valeraldehyde or 2-propylheptanal.
Preferably, the hydrocarbons comprising the second mixture include ethane.
In the present invention, when the higher alcohol product is 2 to PH, the composition of the second mixture is preferably purified and reused.
Preferably, the mass percentage of the higher alcohol in the second component purified liquid in the 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 recited values, and other values not recited in the range of the values are also applicable.
Preferably, the content of the higher alcohol active intermediate component in the second component purified liquid in step (2) is 29 to 30% by mass, for example, 29%, 29.1%, 29.2%, 29.3%, 29.4%, 29.5%, 29.6%, 29.7%, 29.8%, 29.9% or 30% by mass, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the mass percentage of the organic substance having a carbon number smaller than that of the higher alcohol in the second component purified liquid in the step (2) is less than 0.1%, and for example, it 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 values listed, and other values not listed in the range of values are also applicable.
Preferably, the recovery rate of higher alcohols in the second component purified liquid in step (2) is 99% or more, and may be, for example, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8% or 99.9%, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
In the invention, when the high-carbon alcohol product is 2-PH, the composition of the second component purification solution is preferably purified and recycled.
Preferably, the second rectification purification of step (2) is operated at a pressure of 5 to 6kPa, such as 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 recited values, and other values not recited in the range of values 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 pressure reduction 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 not limited to the recited values, and other values not recited in the numerical range are also applicable.
In the invention, the temperature of the second rectification and purification is preferably controlled to be 130-150 ℃, so that the stability of the rectification product can be better ensured, and the reactions such as decomposition and the like due to overtemperature can be avoided.
Preferably, the condensation temperature of the second rectification purification is 40 to 60 ℃, for example 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃ or 60 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
In the present invention, it is preferable to control the condensation temperature of the second rectification purification to 40 to 60 ℃ in order to reduce the treatment cost while cooling the material.
Preferably, the higher alcohol in step (3) includes an alcohol with a carbon number of 4 or more.
Preferably, the higher alcohol comprises any one of butanol, octanol or 2-propylheptanol, preferably 2-propylheptanol.
Preferably, the first component purified liquid in the step (3) is pressurized before being subjected to hydrofining.
Preferably, the first component purified liquid in step (3) is pressurized at an operating pressure of 2 to 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 values not listed in the range of values are also applicable, preferably 2.5 to 3 MPa.
Preferably, the second component purified liquid in the step (3) is pressurized before being subjected to hydrofining.
Preferably, the second component purified liquid in step (3) is pressurized at an operating pressure of 2 to 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 values not listed in the range of values are also applicable, preferably 2.5 to 3 MPa.
In the invention, the first component purification liquid and the second component purification liquid can be respectively subjected to hydrofining, and can also be converged to obtain a recycled material flow for hydrofining, when the hydrofining is carried out after the convergence, the first component purification liquid and the second component purification liquid need to be pressurized before the convergence, and the operation pressures are the same.
In a second aspect, the present invention provides an apparatus system for purifying and recycling waste alcohol in high alcohol production, the apparatus system is used for completing the method for purifying and recycling waste alcohol in high alcohol production according to the first aspect of the present invention; the device system comprises a first rectifying tower, a second rectifying tower and a hydrogenation unit, wherein a discharge port at the top 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 first rectifying tower, the second rectifying tower and the device system of the hydrogenation unit, on one hand, the first rectifying tower and the second rectifying tower are used for re-purifying the first mixture and the second mixture separated from the hydrogenation unit, so that the purpose of purifying the waste alcohol liquid generated by the hydrogenation unit can be realized, on the other hand, the tower top discharge port of the first rectifying tower and the tower kettle discharge port of the second rectifying tower are connected with the hydrogenation unit, so that the obtained first component purified liquid and second component purified liquid can be returned to the hydrogenation unit again for refining, wherein the high-carbon alcohol activity intermediate component can be converted into high-carbon alcohol through re-hydrogenation, 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 material.
Preferably, a tower kettle discharge port of the third rectifying tower is connected with a feed port of the first rectifying tower.
Preferably, the top discharge hole of the fourth rectifying tower is connected with the feed inlet of the second rectifying tower.
Preferably, the discharge hole at the top of the first rectifying tower is connected with the feed inlet of the first hydrogenation reactor or the second hydrogenation reactor, and is preferably connected with the feed inlet of the first hydrogenation reactor.
Preferably, a tower kettle discharge port of the second rectifying tower is connected with a feed port of the first hydrogenation reactor or the second hydrogenation reactor, and is preferably connected with a feed port of the first hydrogenation reactor.
In the invention, the tower top discharge hole of the first rectifying tower and the tower bottom discharge hole of the second rectifying tower are preferably connected with the feed inlet of the first hydrogenation reactor, and the first component purified liquid and the second component purified liquid can be subjected to twice hydrofining, so that the active intermediate components in the first component purified liquid and the second component purified liquid are converted into high-carbon alcohol products to the maximum 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, wherein the recovery rate of the high-carbon alcohol after the obtained first component purified liquid and second component purified liquid are subjected to hydrofining again can reach more than 99 percent, 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 high-carbon alcohol, realizes yield increase and efficiency increase, and can be industrially popularized.
Drawings
FIG. 1 is a process flow diagram of the 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 the 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 column; 3-a second hydrogenation reactor; 4-a fourth rectification column; 5-a second rectification column; 6-first rectifying tower.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a device system for purifying and recycling waste alcohol in high-carbon alcohol production, as shown in fig. 1, the device system 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; 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 reaction raw materials; a tower kettle discharge port of the third rectifying tower 2 is connected with a feed port of the first rectifying tower 6; a discharge hole at the top of the fourth rectifying tower 4 is connected with a feed hole of the second rectifying tower 5; the discharge port of the top of the first rectifying tower 6 and the discharge port of the bottom of the second rectifying tower 5 are connected with the first hydrogenation reactor 1.
The embodiment also provides a method for purifying and recycling the waste alcohol in the high-carbon alcohol production by using the device system for purifying and recycling the waste alcohol in the high-carbon alcohol production, which comprises the following steps:
(1)6000kg/h of first mixture obtained after primary hydrogenation separation of C10 olefine aldehyde is subjected to first rectification purification at 158 ℃ under 5.2kPa (absolute pressure), the temperature of an overhead condenser is 60 ℃, and a first component purification solution containing organic matters with the carbon atoms equivalent to 2-PH carbon atoms is obtained, wherein the first mixture contains 80% of alcohols (including 60% of 2-PH, 11.4% of 2-propyl heptenol, 5% of C13 alcohol and 3.6% of C15 alcohol), 0.4% of 2-propyl heptaldehyde and 19.6% of ketones (including 8% of C10 ketone, 3% of C13 ketone and 8.6% of C15 ketone) by mass percent, and the 2-PH mass percent is 60%;
(2) performing second rectification purification on the second mixture after the secondary hydrogenation separation at the absolute pressure of 5.5kPa and the temperature of an overhead condenser of 60 ℃ at 150 ℃ to obtain a second component purified liquid containing organic matters with the carbon atoms equivalent to 2-PH carbon atoms, wherein the second mixture contains 93% by mass of alcohols (including 25% of 2-PH, 14.3% of pentanol, 12.3% of 2,2, 4-trimethyl-3-pentanol, 17.9% of 2-methyl-2-hexanol, 13.5% of octanol and 10% of 2-propyl heptenol), 6.5% by mass of C10 ketone, 0.4% by mass of aldehydes (including 0.1% by mass of valeraldehyde and 0.3% by mass of 2-propyl heptdehyde) and 0.1% by mass of ethane, wherein the 2-PH mass percentage is 25%;
(3) and pressurizing the first component purified liquid and the second component purified liquid to 2.9MPa respectively, and converging to obtain a recycled material flow, and performing hydrofining to obtain 2-PH.
Example 2
The embodiment provides a device system for purifying and recycling waste alcohol in high-carbon alcohol production, as shown in fig. 2, the device system 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; 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 reaction raw materials; a tower kettle discharge port of the third rectifying tower 2 is connected with a feed port of the first rectifying tower 6; a discharge hole at the top of the fourth rectifying tower 4 is connected with a feed hole of the second rectifying tower 5; the discharge port of the top of the first rectifying tower 6 and the discharge port of the bottom of the second rectifying tower 5 are connected with the second hydrogenation reactor 3.
The embodiment also provides a method for purifying and recycling the waste alcohol in the high-carbon alcohol production by using the device system for purifying and recycling the waste alcohol in the high-carbon alcohol production, which comprises the following steps:
(1)7000kg/h of first mixture obtained after the primary hydro-separation of C10 enal is subjected to primary rectification purification at 156 ℃ under 5.1kPa (absolute pressure), and the temperature of an overhead condenser is 60 ℃ to obtain a first component purified liquid containing organic matters with the carbon atoms equivalent to 2-PH carbon atoms, wherein the first mixture contains 77% of alcohols (including 58% of 2-PH, 10.4% of 2-propylheptenol, 5% of C13 alcohol and 3.6% of C15 alcohol), 1.1% of 2-propylheptanal and 21.9% of ketones (including 9% of C10 ketone, 4% of C13 ketone and 8.9% of C15 ketone) by mass percent, and the 2-PH mass percent is 58%;
(2) a second fraction of the second mixture after the second hydrogenation separation, which contains 94% by mass of alcohols (including 23% of 2-PH, 14.1% of pentanol, 13.6% of 2,2, 4-trimethyl-3-pentanol, 17.8% of 2-methyl-2-hexanol, 14.5% of octanol and 11% of 2-propylheptenol), 5.5% by mass of C10 ketone, 0.45% by mass of aldehydes (including 0.1% by mass of valeraldehyde and 0.3% by mass of 2-propylheptaldehyde) and 0.05% by mass of ethane, is subjected to a second rectification at 148 ℃ under 5.4kPa (absolute pressure) to obtain a second fraction purified liquid containing organic substances having a carbon number equivalent to 2-PH, the temperature of the overhead condenser being 60 ℃;
(3) pressurizing the first component purified liquid and the second component purified liquid to 3.0MPa respectively, and converging to obtain a recycled material flow, and performing 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 embodiment 1, and the method comprises the following steps:
(1)6000kg/h of first mixture obtained after primary hydrogenation separation of C10 enal is subjected to first rectification purification at 7kPa (absolute pressure) and 170 ℃, the temperature of an overhead condenser is 60 ℃, and first component purified liquid containing organic matters with the carbon atoms equivalent to 2-PH carbon atoms is obtained, wherein the first mixture contains 72% of alcohols (including 50% of 2-PH, 11.4% of 2-propyl heptenol, 6% of C13 alcohol and 4.6% of C15 alcohol), 2% of 2-propyl heptenal and 26% of ketones (including 11% of C10 ketone, 6% of C13 ketone and 9% of C15 ketone) by mass percent, wherein the 2-PH mass percent is 50%;
(2) performing second rectification purification on the second mixture after the secondary hydrogenation separation at the absolute pressure of 7kPa and the temperature of 160 ℃ to obtain a second component purified liquid containing organic matters with the carbon atoms equivalent to 2-PH carbon atoms, wherein the second component purified liquid contains 93 percent of alcohols (including 20 percent of 2-PH, 15.1 percent of pentanol, 14.6 percent of 2,2, 4-trimethyl-3-pentanol, 17.8 percent of 2-methyl-2-hexanol, 14.5 percent of octanol and 11 percent of 2-propyl heptenol), 6.5 percent of C10 ketone, 0.45 percent of aldehydes (including 0.1 percent of valeraldehyde and 0.3 percent of 2-propyl heptaldehyde) and 0.05 percent of ethane by mass percentage, and the temperature of an overhead condenser is 60 ℃, and the second component purified liquid contains the organic matters with the carbon atoms equivalent to 2-PH carbon atoms;
(3) and pressurizing the first component purified liquid and the second component purified liquid to 2MPa respectively, and converging to obtain a recycled material flow, and performing 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 embodiment 1, and the method comprises the following steps:
(1)6000kg/h of first mixture obtained after primary hydrogenation separation of C10 olefine aldehyde is subjected to first rectification purification at 6kPa (absolute pressure) and 161 ℃, the temperature of an overhead condenser is 60 ℃, and a first component purified liquid containing organic matters with the carbon atoms equivalent to 2-PH carbon atoms is obtained, wherein the first mixture contains 77% of alcohols (including 55% of 2-PH, 11.4% of 2-propyl heptenol, 6% of C13 alcohol and 4.6% of C15 alcohol), 2% of 2-propyl heptaldehyde and 21% of ketones (including 11% of C10 ketone, 4% of C13 ketone and 6% of C15 ketone) by mass percent, wherein the 2-PH mass percent is 55%;
(2) carrying out second rectification purification on the second mixture after the secondary hydrogenation separation at 156 ℃ under 6kPa (absolute pressure) to obtain a second component purified liquid containing organic matters with the carbon atoms equivalent to 2-PH carbon atoms, wherein the second component purified liquid contains 96% of alcohols (including 25% of 2-PH, 13.1% of pentanol, 14.6% of 2,2, 4-trimethyl-3-pentanol, 16.8% of 2-methyl-2-hexanol, 14.5% of octanol and 12% of 2-propyl heptenol), 3.5% of C10 ketone, 0.45% of aldehydes (including 0.1% of valeraldehyde and 0.3% of 2-propyl heptaldehyde) and 0.05% of ethane (including 2-PH, 25% by mass);
(3) and pressurizing the first component purified liquid and the second component purified liquid to 2.6MPa respectively, and converging to obtain a recycled material flow, and performing 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 embodiment 1, and the method comprises the following steps:
(1)5000kg/h of first mixture obtained after primary hydro-separation of C8 olefine aldehyde is subjected to first rectification purification at 6kPa (absolute pressure) and 160 ℃, the temperature of an overhead condenser is 60 ℃, and first component purified liquid containing organic matters with the carbon atoms equivalent to those of octanol is obtained, wherein the first mixture contains 68% of alcohols (including 50% of octanol, 6% of C12 alcohol, 12% of C16 alcohol and the like), 22% of aldehydes (including 9% of octanal and 12% of C12 aldehyde) and 10% of ketones (including 8% of C8 ketone and 2% of C12 ketone) by mass percentage, and the octanol mass percentage is 50%;
(2) performing second rectification purification on the second mixture after the second hydrogenation separation at the absolute pressure of 6kPa and the temperature of an overhead condenser of 60 ℃ to obtain a second component purified liquid containing organic matters with the carbon atoms equivalent to those of octanol, wherein the second mixture contains 44% of alcohols (including 22% of octanol, 12% of butanol and 10% of octenol), 42% of aldehydes (including 23% of butyraldehyde and 19% of octanal), 14% of ketones (including 9% of butanone and 5% of octanone) and 22% of octanol by mass percent;
(3) pressurizing the first component purified liquid and the second component purified liquid to 2.5MPa respectively, and converging to obtain a recycled material flow for hydrofining to obtain octanol.
The mass percentage of octanol in the purified liquid of the first component obtained in this example was 60%, the mass percentage of active intermediate component was 39.5%, the mass percentage of octanol in the purified liquid of the second component was 46.3%, the mass percentage of active intermediate component was 53%, and the recovery rate of octanol obtained in this example was 99%.
Comparative example 1
The comparative example provides a method for purifying and recycling waste alcohol in the production of high-carbon alcohol, and compared with the example 1, the method only has the advantage that the pressure of the first rectification purification is 4 kPa.
Comparative example 2
The comparative example provides a method for purifying and recycling waste alcohol in the production of high-carbon alcohol, and compared with the example 1, the method only has the advantage that the pressure of the first rectification purification is 8 kPa.
Comparative example 3
The comparative example provides a method for purifying and recycling waste alcohol in the production of high-carbon alcohol, and compared with the example 1, the method only has the temperature of first rectification purification of 110 ℃.
Comparative example 4
The comparative example provides a method for purifying and recycling waste alcohol in the production of high-carbon alcohol, and compared with the example 1, the method only has the temperature of the first rectification purification of 180 ℃.
Comparative example 5
The comparative example provides a method for purifying and recycling waste alcohol in the production of high-carbon alcohol, and compared with the example 1, the method only has the pressure of the second rectification purification of 4 kPa.
Comparative example 6
The comparative example provides a method for purifying and recycling waste alcohol in the production of high-carbon alcohol, and compared with the example 1, the method only has the pressure of the second rectification purification of 8 kPa.
Comparative example 7
The comparative example provides a method for purifying and recycling waste alcohol in the production of high-carbon alcohol, and compared with the example 1, the method only has the temperature of the second rectification purification of 110 ℃.
Comparative example 8
The comparative example provides a method for purifying and recycling waste alcohol in the production of high-carbon alcohol, and compared with the example 1, the method only has the temperature of 170 ℃ for second rectification and purification.
The mass percentage of 2-PH in the first-component purified liquids and the second-component purified liquids obtained in examples 1 to 4 and comparative examples 1 to 8 was measured by shimadzu gas chromatography (GC Smart, GC-2018), and the results are shown in table 1.
The mass percentage of the 2-PH active intermediate component in the first-component purified liquids and the second-component purified liquids obtained in examples 1 to 4 and comparative examples 1 to 8 was measured by shimadzu gas chromatography (GC Smart, GC-2018), and the results are shown in table 1.
The purification and recycling of waste alcohol in examples 1 to 4 and comparative examples 1 to 8 was simulated by Aspen Plus, and the recovery rate of 2-PH was as shown in Table 1.
TABLE 1
It can be seen from the combination of example 1 and comparative examples 1-2 that the pressure of the first rectification purification is 5.2kPa, the recovery rate of the higher alcohol in example 1 is 99.2% compared to 4kPa and 8kPa in comparative example 1 and comparative example 2, respectively, while the recovery rate of the higher alcohol in comparative example 1 is only 94.8%, and the operation cost is very high; the recovery rate of higher alcohol in comparative example 2 was only 89.0%, thus showing that the present invention can improve the recovery rate of higher alcohol 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 3-4 that the temperature of the first rectification purification is 156 ℃, the recovery rate of the higher alcohol in example 1 is 99.2% compared with the recovery rate of the higher alcohol in comparative example 3 and 180 ℃ compared with 110 ℃ and 180 ℃ respectively in comparative example 3 and comparative example 4, the recovery rate of the higher alcohol in comparative example 3 is only 83.8%, the recovery rate of the higher alcohol in comparative example 4 is only 90.1%, and part of the higher alcohol is easily decomposed, thereby showing that the recovery rate of the higher alcohol can be increased and the thermal decomposition of the higher alcohol can be avoided by controlling the temperature of the first rectification purification to be 120 ℃ and 170 ℃.
It can be seen from the combination of example 1 and comparative examples 5 to 6 that the pressure of the second rectification purification is 5.5kPa, the recovery rate of the higher alcohol in example 1 is 99.2% compared to 4kPa and 8kPa in comparative example 5 and comparative example 6, respectively, while the recovery rate of the higher alcohol in comparative example 5 is only 97.9%, and the operation cost is very high; the recovery rate of higher alcohol in comparative example 6 was only 96.8%, thus indicating that the present invention can improve the recovery rate of higher alcohol 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 7-8 that the temperature of the second rectification purification is 150 ℃, the recovery rate of the higher alcohol in example 1 is 99.2% compared to 110 ℃ and 170 ℃ in comparative example 7 and comparative example 8, respectively, the recovery rate of the higher alcohol in comparative example 7 is only 90.7%, the recovery rate of the higher alcohol in comparative example 8 is only 95.5%, and part of the higher alcohol is easily decomposed, thereby indicating that the present invention can improve the recovery rate of the higher alcohol and avoid thermal decomposition of the higher alcohol by controlling the temperature of the second rectification purification to be 120 ℃ and 160 ℃.
In conclusion, the method and the device system for purifying and recycling the waste alcohol in the high-carbon alcohol production can improve the recovery rate of the high-carbon alcohol to more than 99%, reduce the discharge of waste alcohol liquid, improve the yield of the high-carbon alcohol and realize yield increase and efficiency increase.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A method for purifying and recycling waste alcohol in high-carbon alcohol production is characterized by comprising the following steps:
(1) carrying out first rectification and purification on the first mixture subjected to primary hydrogenation separation at the temperature of between 5 and 7kPa and between 120 and 170 ℃ to obtain a first component purification solution containing organic matters with carbon atoms equivalent to those of the high-carbon alcohol; the first mixture comprises organic matter with the carbon number being more than or equal to that of the higher alcohol;
(2) performing second rectification and purification on the second mixture after the secondary hydrogenation separation at the temperature of between 5 and 7kPa and between 120 and 160 ℃ to obtain a second component purification solution containing organic matters with the carbon number equivalent to that of the high-carbon alcohol; the second mixture comprises organic matter with the carbon number less than or equal to that of the high-carbon alcohol;
(3) hydrorefining the first component purified liquid obtained in the step (1) and the second component purified liquid obtained in the step (2) to obtain high-carbon alcohol;
the step (1) and the step (2) have no precedence relationship.
2. The method of claim 1, wherein the higher alcohol is present in the first mixture of step (1) in an amount of 50-60% by weight.
3. The process according to claim 1 or 2, characterized in that the operating pressure of the first rectification purification of step (1) is 5-6 kPa;
preferably, the temperature of the first rectification purification is 130-160 ℃;
preferably, the condensation temperature of the first rectification purification is 40-60 ℃.
4. The method according to any one of claims 1 to 3, wherein the higher alcohol is present in the second mixture in step (2) in an amount of 20 to 30% by mass.
5. The process according to any one of claims 1 to 4, characterized in that the operating pressure of the second rectification purification of step (2) is 5 to 6 kPa;
preferably, the temperature of the second rectification purification is 130-150 ℃;
preferably, the condensation temperature of the second rectification purification is 40-60 ℃.
6. The method according to any one of claims 1 to 5, wherein the higher alcohol in step (3) comprises an alcohol having 4 or more carbon atoms;
preferably, the higher alcohol comprises any one of butanol, octanol or 2-propylheptanol, preferably 2-propylheptanol.
7. The method according to any one of claims 1 to 6, wherein the first component purified liquid in the step (3) is pressurized before being subjected to hydrofinishing;
preferably, the first component purified liquid in the step (3) is pressurized at an operating pressure of 2 to 3.2MPa, preferably 2.5 to 3 MPa;
preferably, the second component purified liquid in the step (3) is pressurized before being subjected to hydrofining;
preferably, the second component purified liquid in the step (3) is pressurized at an operating pressure of 2 to 3.2MPa, preferably 2.5 to 3 MPa.
8. An apparatus system for purifying and recycling waste alcohol in high-carbon alcohol production, which is characterized in that the apparatus system is used for completing the method for purifying and recycling the waste alcohol in the high-carbon alcohol production according to any one of claims 1 to 7;
the device system comprises a first rectifying tower, a second rectifying tower and a hydrogenation unit, wherein a discharge port at the top 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.
9. The apparatus system of claim 8, wherein the hydrogenation unit comprises a first hydrogenation reactor, a third rectification column, a second hydrogenation reactor and a fourth rectification column connected in sequence along the flow direction of the reaction feedstock;
preferably, a tower kettle discharge port of the third rectifying tower is connected with a feed port of the first rectifying tower;
preferably, the top discharge hole of the fourth rectifying tower is connected with the feed inlet of the second rectifying tower.
10. The device system according to claim 9, wherein the top discharge port of the first 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;
preferably, a tower kettle discharge port of the second rectifying tower is connected with a feed port of the first hydrogenation reactor or the second hydrogenation reactor, and is preferably connected with a feed port of the first hydrogenation reactor.
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