CN112794801A - Method for inhibiting byproduct tar in low-pressure carbonyl synthesis acetic anhydride process - Google Patents
Method for inhibiting byproduct tar in low-pressure carbonyl synthesis acetic anhydride process Download PDFInfo
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- CN112794801A CN112794801A CN202110031135.4A CN202110031135A CN112794801A CN 112794801 A CN112794801 A CN 112794801A CN 202110031135 A CN202110031135 A CN 202110031135A CN 112794801 A CN112794801 A CN 112794801A
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- acetic anhydride
- tar
- inhibitor
- reaction
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- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000006227 byproduct Substances 0.000 title claims abstract description 21
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 13
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 title claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000003112 inhibitor Substances 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000007086 side reaction Methods 0.000 claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 8
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 8
- 239000002683 reaction inhibitor Substances 0.000 claims abstract description 5
- MYSWGLZTUMZAAS-UHFFFAOYSA-N [Rh].[I] Chemical compound [Rh].[I] MYSWGLZTUMZAAS-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 oxo acetic anhydride Chemical compound 0.000 claims 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000005810 carbonylation reaction Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000006315 carbonylation Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 47
- 229910002092 carbon dioxide Inorganic materials 0.000 description 25
- 239000001569 carbon dioxide Substances 0.000 description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- TUCNEACPLKLKNU-UHFFFAOYSA-N acetyl Chemical compound C[C]=O TUCNEACPLKLKNU-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 3
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 2
- 125000002934 2-oxopropylidene group Chemical group 0.000 description 2
- AUZFRUHVDNDVJI-UHFFFAOYSA-N 3-acetylpentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)C(C)=O AUZFRUHVDNDVJI-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- CTHCTLCNUREAJV-UHFFFAOYSA-N heptane-2,4,6-trione Chemical compound CC(=O)CC(=O)CC(C)=O CTHCTLCNUREAJV-UHFFFAOYSA-N 0.000 description 2
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 2
- BHVICADLOSIXKE-UHFFFAOYSA-N oxaldehydoyl 2-oxoacetate Chemical compound O=CC(=O)OC(=O)C=O BHVICADLOSIXKE-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/54—Preparation of carboxylic acid anhydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/54—Preparation of carboxylic acid anhydrides
- C07C51/573—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for inhibiting byproduct tar in a process of synthesizing acetic anhydride by low-pressure carbonyl, which comprises the steps of adding a side reaction inhibitor into a reaction system of a one-step method acetic anhydride oxo synthesis process under a rhodium-iodine catalyst system by taking methanol and carbon monoxide as raw materials, thereby inhibiting the byproduct tar radically; the inhibitor is CO2(ii) a By adopting the technical scheme, on the premise of not changing a catalyst system and a process route, CO is added into a reaction system2As an inhibitor of side reaction, the method inhibits the reaction from proceeding at the source of the side reaction, reduces the rate of tar generation by the side reaction, can keep the stability and activity of the catalyst, and is easy to circularly separate, thereby prolonging the production period of the process for producing acetic anhydride by a carbonylation method.
Description
Technical Field
The invention relates to a method for inhibiting byproduct tar, in particular to a method for inhibiting byproduct tar in a process of synthesizing acetic anhydride by low-pressure carbonyl.
Background
In the prior art, the production process of oxo-acetic anhydride is a high-temperature anhydrous carbonylation system, complex side reactions can occur in the reaction system, a plurality of byproducts with long carbon chains are generated and collectively called as tar, the greatest harm is to wrap a catalyst and an auxiliary agent, the reaction activity is reduced, the catalytic activity is completely lost when the catalyst and the auxiliary agent are serious, and meanwhile, the material is sticky and solidified due to high-content tar, so that a pipeline and a pump are easily blocked, and the production is stopped rapidly.
The prior process for producing acetic anhydride by adopting a carbonylation method always suffers from a problem that tar in a system is gradually accumulated, and the full-load long-period operation of a device is seriously restricted.
Researches find that in an acetic anhydride oxo-synthesis system, the cracking of acetic anhydride can generate acetone, the acetone can react with acetic anhydride and acetaldehyde in a carbonylation reaction system, and the derivatives of the acetone are various and become an important source of tar.
CH3COCH3+(CH3CO)2O→(CH3CO)2CH2(acetylacetone) + CH3COOH ①
CH3COCH3+(CH3CO)2O→(CH3COCH2)2CO (diacetylacetone) + H2O ②
CH3COCH3+(CH3CO)2O→(CH3CO)3CH (1, 1-diacetylacetone) + H2O ③
(CH3CO)2CH2(Acetylacetone) + (CH)3CO)2O→CH3COOC(CH3)→CHCOCH3 ④
CH3COCH3+CH3COOH→(CH3CO)2CH2(acetylacetone) + H2O ⑤
CH3COCH3+2CH3COOH→(CH3COCH2)2CO (diacetylacetone) +2H2O ⑥
CH3COCH3+2CH3COOH→(CH3CO)3CH (1, 1-diacetylacetone) +2H2O ⑦
Acetone is easy to self-condense to generate polymer compound 2CH under the high-temperature anhydrous condition of 180 DEG C3COCH3(Anhydrous, 180 ℃ C.) → CH3COCH2C(CH3)2OH (diacetone alcohol) (+)
Dimers, and also trimeric tetramers, etc. (heating),
CH3-CO-CH＝C(CH3)2(mesityl oxide) + H2O ⑨
2CH3COCH3+(CH3CO)2O→CH3-CO-CH＝C(CH3)2
(mesityl oxide ) +2CH3COOH ⑩
Disclosure of Invention
In view of the above, the main object of the present invention is to provide a method for inhibiting by-product tar in the process of synthesizing acetic anhydride by low pressure carbonyl, wherein by the technical scheme, CO is added into the reaction system without changing the catalyst system and the process route2As side reaction inhibitor, can inhibit the reaction from proceeding at the source of side reaction, reduce the rate of tar formation by side reaction, maintain the stability and activity of catalyst, andand the method is easy to circularly separate, thereby prolonging the production period of the process for producing acetic anhydride by the carbonylation method.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a method for inhibiting by-product tar in the process of synthesizing acetic anhydride by low-pressure carbonyl is characterized in that methanol and carbon monoxide are used as raw materials, and a side reaction inhibitor is added into a reaction system of the process of synthesizing acetic anhydride by one-step carbonyl under a rhodium-iodine catalyst system, so that the by-product tar is radically inhibited.
As a further technical scheme, the inhibitor is CO2。
As a further technical scheme, the inhibitor is added into raw material gas.
As a further technical scheme, the inhibitor is added into the reactor.
As a further technical proposal, the inhibitor is added into raw material gas, and CO is used as the inhibitor2The content of the raw material gas is 0.1-4%.
As a further technical proposal, the inhibitor is added into the reactor, and CO is used as the inhibitor2The content of the catalyst in the reactor is 0.5-16%.
The beneficial effect after adopting above-mentioned technical scheme is: the technological scheme of inhibiting by-product tar in low pressure oxo process of synthesizing acetic anhydride includes adding CO into the reaction system without altering the catalyst system and technological path2As an inhibitor of side reaction, the method inhibits the reaction from proceeding at the source of the side reaction, reduces the rate of tar generation by the side reaction, can keep the stability and activity of the catalyst, and is easy to circularly separate, thereby prolonging the production period of the process for producing acetic anhydride by a carbonylation method.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The invention relates to a method for inhibiting byproduct tar in a process of synthesizing acetic anhydride by low-pressure carbonyl, which is characterized in that a side reaction inhibitor is added into a reaction system of a one-step method acetic anhydride oxo synthesis process under a rhodium-iodine catalyst system by taking methanol and carbon monoxide as raw materials, so that the byproduct tar is radically inhibited.
As a further example, the inhibitor is CO2。
As a further example, the inhibitor is added to the feed gas.
As a further example, the inhibitor is added within the reactor.
As a further example, the inhibitor is added to the feed gas, CO being the inhibitor2The content of the raw material gas is 0.1-4%.
As a further example, the inhibitor is added in the reactor, CO being the inhibitor2The content of the catalyst in the reactor is 0.5-16%.
The invention introduces high-purity carbon dioxide into the production system of the oxo-acetic anhydride, and the high-purity carbon dioxide can be blown along with the raw material gas, the adding amount of the carbon dioxide is controlled, and a certain amount of emptying is kept simultaneously, so as to keep the content of the carbon dioxide in the reaction system stable.
The certain amount of carbon dioxide in the reaction system can inhibit the cracking reaction, thereby radically inhibiting the generation of the byproduct acetone and achieving the purpose of reducing the byproduct tar.
In the carbonylation reaction system, the partial pressure of carbon monoxide influences the activity and stability of the catalyst, and the introduction amount of the inhibitor carbon dioxide is obtained through calculation on the premise of not influencing the partial pressure of the carbon monoxide.
Wherein the partial pressure of carbon monoxide is calculated as PCO＝((P+0.1)*(1-Y+0.1344*(γ(CH3I)P(CH3I)*X(CH3I)))*CO v％/100。
Wherein the CO v% is CO in inert tail gas, e.g. N2、H2、CO2、CH4In percentage by volume.
Example 1
According to the process method and the steps of the invention, the content of the carbon dioxide added into the raw material gas is 0.1 percent, the reaction lasts for 40 hours, the space-time yield of acetic anhydride is 5.61mol/(L x h), the influence is avoided, and the tar increase rate is 40 percent, wherein the tar increase rate refers to the ratio of the tar increase value to the tar content before the reaction.
Example 2
According to the process and the steps of the invention, the content of carbon dioxide added into the feed gas is 3%, the reaction lasts for 40h, and the space-time yield of acetic anhydride is 6.1mol/(L x h), which is not influenced. The tar growth rate, which is defined herein as the ratio of tar increment to the pre-reaction tar content, is 27%.
Example 3
According to the process and the steps of the invention, the content of carbon dioxide added into the raw material gas is 4%, the reaction lasts for 40 hours, and the space-time yield of acetic anhydride is 5.16mol/(L x h), which is not influenced. The tar growth rate, which is referred to herein as the ratio of tar increment to pre-reaction tar content, was 19%.
In conclusion, the increase of the content of carbon dioxide in the feed gas obviously reduces the increase rate of tar, and the space-time yield of acetic anhydride reduces after the content of carbon dioxide reaches 4%.
Example 4:
according to the process and steps of the invention, carbon dioxide is fed to the reactor, wherein the carbon dioxide content is 0.5% in the gas phase of the reactor, and the reaction time is 40h, and the space time yield of acetic anhydride is 5.66mol/(L x h), unaffected. The tar growth rate, which is defined herein as the ratio of tar increase to the pre-reaction tar content, is 39%.
Example 5
According to the process and steps of the invention, carbon dioxide is fed into the reactor, wherein the carbon dioxide content is 4% in the gas phase of the reactor, and the reaction is carried out for 40 h. The time-space yield of acetic anhydride was 5.89mol/(L × h), unaffected, and the tar growth rate, which is the ratio of tar increment to pre-reaction tar content, was 24.5%.
Example 6:
according to the process and steps of the invention, carbon dioxide is fed into the reactor, wherein the carbon dioxide content is 16% in the gas phase of the reactor, the reaction time is 40h, and the space-time yield of acetic anhydride is 4.1mol/(L x h), which is obviously reduced. The tar growth rate, which is referred to herein as the ratio of tar increase to the pre-reaction tar content, is 11%.
In summary, the rate of tar growth has a marked decrease with increasing carbon dioxide content in the reactor, and the space-time yield of acetic anhydride has been shown to decrease as the carbon dioxide content is increased to 16%.
In summary, the addition of carbon dioxide to both the feed gas and directly to the reactor achieves the goal of inhibiting tar growth, but both are accompanied by a decrease in the space time yield of acetic anhydride as the carbon dioxide content increases, indicating that the main reaction is inhibited, and the present invention requires the addition of carbon dioxide at a suitable level that would otherwise affect the partial pressure of carbon monoxide in the reactor, thereby resulting in a limitation of the main reaction of acetic anhydride.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention.
Claims (6)
1. A method for inhibiting byproduct tar in a process of synthesizing acetic anhydride by low-pressure carbonyl is characterized in that a side reaction inhibitor is added into a reaction system of a one-step method acetic anhydride oxo synthesis process under a rhodium-iodine catalyst system by taking methanol and carbon monoxide as raw materials, so that the byproduct tar is radically inhibited.
2. The method of claim 1, wherein said inhibitor is CO, and said inhibitor is CO2。
3. The method for suppressing by-product tar in the process for the low pressure oxo synthesis of acetic anhydride according to claim 1 or 2, wherein the suppressing agent is added to the raw gas.
4. The method for suppressing by-product tar in the process of oxo acetic anhydride under low pressure according to claim 1 or 2, wherein: the inhibitor is added in the reactor.
5. The method of suppressing byproduct tar in the low pressure oxo acetic anhydride process according to claim 3, wherein the suppressor is added to the feed gas, and CO is used as the suppressor2The content of the raw material gas is 0.1-4%.
6. The method of suppressing byproduct tar in the low pressure oxo acetic anhydride process as claimed in claim 4, wherein said inhibitor is added in the reactor, CO is used as the inhibitor2The content of the catalyst in the reactor is 0.5-16%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110031135.4A CN112794801A (en) | 2021-01-11 | 2021-01-11 | Method for inhibiting byproduct tar in low-pressure carbonyl synthesis acetic anhydride process |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110031135.4A CN112794801A (en) | 2021-01-11 | 2021-01-11 | Method for inhibiting byproduct tar in low-pressure carbonyl synthesis acetic anhydride process |
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| CN112794801A true CN112794801A (en) | 2021-05-14 |
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| CN202110031135.4A Pending CN112794801A (en) | 2021-01-11 | 2021-01-11 | Method for inhibiting byproduct tar in low-pressure carbonyl synthesis acetic anhydride process |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR940008742A (en) * | 1992-10-30 | 1994-05-16 | 서정욱 | Combined method of methyl acetate, acetic acid and acetic anhydride |
| CN1228408A (en) * | 1998-01-31 | 1999-09-15 | 英国石油化学品有限公司 | Anhydrous carbonylation process for production of acetic acid |
| CN1939586A (en) * | 2005-09-28 | 2007-04-04 | 中国科学院化学研究所 | Homogeneous rhodium catalytic system of oxo-acetic anhydride and its use |
| US20190002386A1 (en) * | 2017-06-30 | 2019-01-03 | Lyondellbasell Acetyls, Llc | Reaction control in acetic acid processes |
-
2021
- 2021-01-11 CN CN202110031135.4A patent/CN112794801A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR940008742A (en) * | 1992-10-30 | 1994-05-16 | 서정욱 | Combined method of methyl acetate, acetic acid and acetic anhydride |
| CN1228408A (en) * | 1998-01-31 | 1999-09-15 | 英国石油化学品有限公司 | Anhydrous carbonylation process for production of acetic acid |
| CN1939586A (en) * | 2005-09-28 | 2007-04-04 | 中国科学院化学研究所 | Homogeneous rhodium catalytic system of oxo-acetic anhydride and its use |
| US20190002386A1 (en) * | 2017-06-30 | 2019-01-03 | Lyondellbasell Acetyls, Llc | Reaction control in acetic acid processes |
Non-Patent Citations (1)
| Title |
|---|
| 夏春华等: ""羰基合成醋酐反应中抑制焦油生成的新方法"", 《乙醛醋酸化工》 * |
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