CN1340495A - Process for preparing orthoformate from hydrocyanic acid as waste gas of acrylonitrile plant - Google Patents
Process for preparing orthoformate from hydrocyanic acid as waste gas of acrylonitrile plant Download PDFInfo
- Publication number
- CN1340495A CN1340495A CN 00111314 CN00111314A CN1340495A CN 1340495 A CN1340495 A CN 1340495A CN 00111314 CN00111314 CN 00111314 CN 00111314 A CN00111314 A CN 00111314A CN 1340495 A CN1340495 A CN 1340495A
- Authority
- CN
- China
- Prior art keywords
- content
- purity
- temperature
- orthoformate
- hydrocyanic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for preparing orthoformate from the hydrocyanic acid as the waste gas of acrylonitrile plant includes such steps as reaction of hydrocyanic acid as initial raw material on corresponding alcohol and halogen acid in inertial solvent through forming salt, alcoholysis, crystallizing, separation and rectifying to obtain trimethyl orthoformate with methanol or triethyl orthoformate with ethanol. Its advantages include low cost, high output rate and quality, and use of waste as raw material.
Description
The invention belongs to the technical field of environmental protection, and relates to a process for preparing orthoformate by using hydrocyanic acid discharged from an acrylonitrile plant.
In the acrylonitrile production process, a large amount of hydrocyanic acid-containing waste gas (the amount of hydrocyanic acid is about 70-95%, the balance is 2.0-28% of nitrogen, 1.0-1.5% of ammonia and 1.0-1.5% of propylene) is discharged, the annual discharge amount of acrylonitrile plants of the Qilu petrochemical company is about 4800 tons, and the traditional treatment method is to utilize the byproduct sodium cyanide.
The traditional treatment method has the defects of low added value of the by-product and resource waste.
The invention aims to comprehensively utilize hydrocyanic acid in waste gas discharged from an acrylonitrile plant as a raw material to prepare an important organic intermediate orthoformate which has wide application in industries such as chemical industry, medicine, pesticide, dye, spice and the like.
The traditional process for preparing orthoformate is to react corresponding sodium alkoxide with chloroform to prepare corresponding orthoformate:
the process for preparing orthoformate comprises the steps of adding hydrocyanic acid and corresponding alcohol to generate salt, and preparing the corresponding orthoformate through alcoholysis:
the present invention relates to a process for producing orthoformate by hydrocyanic acid method, which is characterized in that hydrocyanic acid is used as initial raw material, and the raw material is prepared by salifying, alcoholysis, crystallization separation and rectification with corresponding alcohol and halogen acid in inert solvent (such as solvent naphtha, cyclohexane, normal heptane, etc.),
the molar ratio of the reaction materials is that hydrocyanic acid, corresponding alcohol and halogen acid is 1: 3.5-4.0: 1.1-1.25
The reaction temperature of the salifying step is-20-10 ℃, the reaction temperature of the alcoholysis step is 30-60 ℃, and the reaction time is 24-72 hours.
Trimethyl orthoformate can be prepared by using methanol; triethyl orthoformate can be prepared using ethanol.
Compared with the traditional orthoformate preparation process, the method has the advantages that:
1. the resources are comprehensively utilized, the waste is changed into valuable, and the environment protection is facilitated;
2. low cost, high yield and good quality; the traditional process for preparing orthoformate has the raw material cost of 2.1 ten thousand yuan/ton, the yield of 60-65 percent and the content of 97 percent +/-minus or plus; the process has the advantages of 1.1 ten thousand yuan per ton of raw materials, 75-80% of yield and more than 98% of content.
The invention is further illustrated below with reference to process flows and examples.
And (2) uniformly mixing hydrocyanic acid and the first part of corresponding alcohol in an inert solvent, cooling to a specified temperature, introducing a hydrogen halide gas, maintaining the reaction temperature, maintaining the temperature until imine salt is separated out, adding the second part of corresponding alcohol after the imine salt is completely separated out, adjusting the pH value of a reaction solution to be 0.5-3.0, keeping the temperature to be 30-60 ℃, reacting for 24-72 hours, removing ammonium halide after alcoholysis is finished, evaporating the solvent, and rectifying to obtain a finished orthoformate product.
Example one reaction mass molar ratio was hydrocyanic acid to ethanol to hydrobromic acid 1: 3.5: 1.1.
Feeding 218.18kg of HCN (the content of which is 99 percent, converted into pure 216kg and 8kmol), 443.8kg of absolute ethyl alcohol (the content of which is 99.5 percent, converted into pure 441.6kg and 9.6kmol) and 2000L of solvent oil into a reactionkettle, uniformly stirring, cooling to-10 ℃, uniformly introducing 712.8kg of hydrogen bromide gas, maintaining the temperature between-10 ℃ and-20 ℃ in the reaction process, maintaining the temperature after the reaction is finished, completely separating out the imine salt, adding 850.6kg of absolute ethyl alcohol (the content of which is 99.5 percent, converted into pure 846.4kg and 18.4kmol) into the reaction kettle, adjusting the pH of the reaction solution to 0.5-3.0, maintaining the temperature to 50-60 ℃, reacting for 48 hours, removing ammonium bromide after alcoholysis is finished, distilling off the solvent to obtain 984.67kg of triethyl orthoformate, determining the content of which is 99.20 percent by chromatography, converted into pure 976.8kg and obtaining the yield of 82.5 percent.
Example two reaction feeds were in a molar ratio of hydrocyanic acid to ethanol to hydrobromic acid of 1: 3.8: 1.2.
Feeding 218.18kg of HCN (the content is 99%, the purity is 216kg, 8kmol), 517.7kg of anhydrous ethanol (the content is 99.5%, the purity is 515.2kg, 11.2kmol), cooling to-5 ℃, introducing 777.6kg of hydrogen bromide gas, reacting at the temperature of-5 to-10 ℃, maintaining the temperature after introduction is finished, adding 887.6kg of anhydrous ethanol (the content is 99.5%, the purity is 883.2kg, 19.2kmol) after the imine salt is completely separated out, keeping the temperature at 40-50 ℃, reacting for 24 hours to obtain 964.84kg of a finished product of the triethyl orthoformate, determining the content by chromatography to be 99.03%, the purity is 955.5kg, and the yield is 80.7%. The rest is the same as the first embodiment.
The molar ratio of the reaction mass of example three was 1: 3.75: 1.25 hydrocyanic acid to ethanol to hydrobromic acid.
Feeding 218.18kg of HCN (the content is 99%, the purity is 216kg, 8kmol), 499.2kg of anhydrous ethanol (thecontent is 99.5%, the purity is 496.8kg, 10.8kmol), using cyclohexane as an inert solvent, cooling to 5 ℃, introducing 810kg of hydrogen bromide gas, reacting at 5-10 ℃, maintaining the temperature after introducing is finished, adding 887.6kg of anhydrous ethanol (the content is 99.5%, the purity is 883.2kg, 19.2kmol) after the imine salt is completely separated out, maintaining the temperature at 30-40 ℃, and reacting for 36 hours to obtain 919.24kg of a finished triethyl orthoformate product, the content is 98.92%, the purity is 909.3kg, and the yield is 76.8%. The rest is the same as the first embodiment.
Example four reaction feeds were in a molar ratio of hydrocyanic acid to ethanol to hydrobromic acid of 1: 4.0: 1.3.
218.18kg of HCN (content 99%, pure 216kg, 8kmol), 554.7kg of anhydrous ethanol (content 99.5%, pure 552.0kg, 12.0kmol) as a first part, cyclohexane as an inert solvent, cooling to-10 ℃, introducing 842.4kg of hydrogen bromide gas, reacting at-10 to-20 ℃, maintaining the temperature after the introduction is finished, completely separating out the imine salt, adding 924.6kg of anhydrous ethanol (content 99.5%, pure 920.0kg, 20.0kmol) as a second part, maintaining the temperature at 40-50 ℃, and reacting for 60 hours to obtain 925.43kg of a finished triethyl orthoformate product, wherein the content is 98.77%, the content is 914.0kg, and the yield is 77.2%. The rest is the same as the first embodiment.
Example five the molar ratio of reaction mass was 1: 3.6: 1.25 hydrocyanic acid to ethanol to hydrobromic acid.
Feeding 218.18kg of HCN (the content is 99%, the purity is 216kg, 8kmol), 480.8kg of anhydrous ethanol (the content is 99.5%, the purity is 478.4kg, 10.4kmol), reducing the temperature to-5 ℃ by using cyclohexane as an inert solvent, introducing 810kg of hydrogen bromide gas, reacting at the temperature of-5 to-10 ℃,maintaining the temperature after introducing is finished, completely separating out imine salt, adding 850.6kg of anhydrous ethanol (the content is 99.5%, the purity is 846.4kg, 18.4kmol), maintaining the temperature at 30-40 ℃, and reacting for 24 hours to obtain 905.77kg of triethyl orthoformate finished product, the content is 98.56%, the purity is 892.7kg, and the yield is 75.4%. The rest is the same as the first embodiment.
Example the molar ratio of the six reaction feeds was hydrocyanic acid to ethanol to hydrobromic acid 1: 3.75: 1.2.
Feeding 218.18kg of HCN (the content is 99%, the purity is 216kg, 8kmol), 462.3kg of anhydrous ethanol (the content is 99.5%, the purity is 460.0kg, 10.0kmol) in the first part, cooling to-5 ℃, introducing 777.6kg of hydrogen bromide gas, reacting at the temperature of-5 to-10 ℃, maintaining the temperature after introducing is finished, adding 924.6kg of anhydrous ethanol (the content is 99.5%, the purity is 920.0kg, 20.0kmol) in the second part after imine salt is completely separated out, keeping the temperature at 40-50 ℃, and reacting for 72 hours to obtain 948.3kg of a finished product of triethyl orthoformate, the content is 99.01%, the purity is 938.9kg, and the yield is 79.3%. The rest is the same as the first embodiment.
Example seven reaction feeds were prepared in a molar ratio of hydrocyanic acid to ethanol to hydrobromic acid of 1: 3.8: 1.1.
218.18kg of HCN (content 99%, purity 216kg, 8kmol), 480.8kg of anhydrous ethanol (content 99.5%, purity 478.4kg, 10.4kmol) as a first part, cooling to-5 ℃ by using n-heptane as an inert solvent, introducing 712.8kg of hydrogen bromide gas, reacting at-5 ℃, maintaining the temperature after the introduction is finished, completely separating out imine salt, adding 924.6kg of anhydrous ethanol (content 99.5%, purity 920.0kg, 20.0kmol) as a second part, keeping the temperature at50-60 ℃, and reacting for 60 hours to obtain 957.4kg of triethyl orthoformate finished product, 99.05%, purity 948.38kg and 80.1% of yield. The rest is the same as the first embodiment.
Example eight reaction feeds were in a molar ratio of hydrocyanic acid to ethanol to hydrobromic acid of 1: 4.0: 1.25.
218.18kg of HCN (the content is 99 percent, the purity is 216kg, 8kmol), 480.8kg of anhydrous ethanol (the content is 99.5 percent, the purity is 478.4kg, 10.4kmol), n-heptane is used as an inert solvent, the temperature is reduced to-10 ℃, hydrogen bromide gas is introduced into the mixture at 810.0kg, the reaction temperature is-10 to-15 ℃, after the introduction is finished, the temperature is maintained, after the imine salt is completely separated out, 998.5kg of anhydrous ethanol (the content is 99.5 percent, the purity is 993.6kg, 21.6kmol) is added into the mixture, the temperature is maintained at 40-50 ℃, and the reaction is carried out for 48 hours, so that a finished triethyl orthoformate product 984.4kg, the content is 98.98 percent, the purity is 974.4kg, and the yield is 82.3 percent is. The rest is the same as the first embodiment.
Example nine the molar ratio of reaction mass was hydrocyanic acid to ethanol to hydrobromic acid 1: 3.8: 1.2.
218.18kg of HCN (content 99%, purity 216kg, 8kmol), 480.8kg of anhydrous ethanol (content 99.5%, purity 478.4kg, 10.4kmol) as a first part, cooling to 0 ℃ by using n-heptane as an inert solvent, introducing 777.6kg of hydrogen bromide gas, reacting at 0-10 ℃, maintaining the temperature after the introduction is finished, and after imine salt is completely separated out, adding 924.6kg of anhydrous ethanol (content 99.5%, purity 920.0kg, 20kmol) as a second part, keeping the temperature at 30-40 ℃, and reacting for 36 hours to obtain 965.0kg of triethyl orthoformate finished product, 98.56%,purity 931.8kg, and yield 78.7%. The rest is the same as the first embodiment.
Example the molar ratio of reaction mass was 1: 3.75: 1.3 hydrocyanic acid to ethanol to hydrobromic acid.
218.18kg of HCN (content 99%, purity 216kg, 8kmol), 499.2kg of anhydrous ethanol (content 99.5%, purity 496.8kg, 10.8kmol) are added, the temperature is reduced to-5 ℃, 842.4kg of hydrogen bromide gas is introduced, the reaction temperature is-5-10 ℃, after introduction is finished, the temperature is maintained, after the imine salt is completely separated out, 887.6kg of anhydrous ethanol (content 99.5%, purity 883.2kg, 19.2kmol) is added, the temperature is maintained at 30-40 ℃, and the reaction is carried out for 24 hours, so that 917kg of the finished triethyl orthoformate product is obtained, the content is 98.64%, the purity 904.5kg and the yield is 76.4%. The rest is the same as the first embodiment.
Example eleven the molar ratio of reaction mass was hydrocyanic acid to methanol to hydrochloric acid 1: 3.5: 1.1.
Feeding 218.18kg of HCN (the content of which is 99 percent, converted into pure 216kg and 8kmol), 308.7kg of anhydrous methanol (the content of which is 99.5 percent, converted into pure 307.2kg and 9.6kmol) and 2000L of solvent oil into a reaction kettle, uniformly stirring, cooling to-10 ℃, uniformly introducing 321.2kg of hydrogen chloride gas, maintaining the temperature to be-10 to-20 ℃ in the reaction process, maintaining the temperature after the reaction is finished, adding 591.7kg of anhydrous methanol (the content of which is 99.5 percent, converted into pure 588.8kg and 18.4kmol) after the imine salt is completely separated out, adjusting the pH of a reaction solution to be 0.5-3.0, maintaining the temperature to be 50-60 ℃, reacting for 48 hours, removing ammonium chloride after alcoholysis is finished, distilling to remove the solvent to obtain 646.4kg of trimethyl orthoformate finished products, measuring the content of which is 99.03 percent by chromatography, converted into pure 640.2kg and obtaining the yield of 75.5 percent.
Example twelve reaction streams are in a molar ratio of hydrocyanic acid to methanol to hydrochloric acid of 1: 3.8: 1.2.
Feeding 218.18kg of HCN (the content is 99%, the purity is 216kg, 8kmol), 360.2kg of anhydrous methanol (the content is 99.5%, the purity is 358.4kg, 11.2kmol), cooling to-5 ℃, introducing 350.4kg of hydrogen chloride gas, reacting at-5 to-10 ℃, maintaining the temperature after introducing is finished, adding 617.4kg of anhydrous methanol (the content is 99.5%, the purity is 614.4kg, 19.2kmol) after the imine salt is completely separated out, maintaining the temperature at 40-50 ℃, reacting for 24 hours to obtain 647.84kg of trimethyl orthoformate finished products, determining the content by chromatography to be 98.56%, the purity is 638.5kg, and the yield is 75.3%. The rest is the same as the eleventh example.
Example thirteen the molar ratio of reaction mass was hydrocyanic acid to methanol to hydrochloric acid 1: 3.75: 1.25.
218.18kg of HCN (content 99%, purity 216kg, 8kmol), 347.3kg of anhydrous methanol (content 99.5%, purity 345.6kg, 10.8kmol) as a first part, cyclohexane as an inert solvent, cooling to 5 ℃, introducing 365kg of hydrogen chloride gas, reacting at 5-10 ℃, maintaining the temperature after introducing is finished, adding 617.4kg of anhydrous methanol (content 99.5%, purity 614.4kg, 19.2kmol) as a second part after imine salt is completely separated out, maintaining the temperature at 30-40 ℃, and reacting for 36 hours to obtain 640.4kg of trimethyl orthoformate finished product, 98.78%, purity 632.6kg and yield 74.6%. The rest is the same as the eleventh example.
Example fourteen reaction masses were mixed in a molar ratio of hydrocyanic acid to methanol to hydrochloric acid of 1: 4.0: 1.3.
218.18kg of HCN (content 99%, pure 216kg, 8kmol), 385.9kg of anhydrous methanol (content 99.5%, pure 384.0kg, 12.0kmol) as the first part, cyclohexane as the inert solvent, cooling to-10 ℃, introducing 379.6kg of hydrogen chloride gas, reacting at-10 to-20 ℃, maintaining the temperature after the introduction is finished, completely separating out the imine salt, adding 643.2kg of anhydrous methanol (content 99.5%, pure 640.0kg, 20.0kmol) as the second part, maintaining the temperature at 40-50 ℃, and reacting for 60 hours to obtain 661.1kg of trimethyl orthoformate finished product, 98.90%, 653.8kg of pure orthoformate and 77.1% of yield. The rest is the same as the eleventh example.
Example fifteen the molar ratio of reaction mass was hydrocyanic acid to methanol to hydrochloric acid 1: 3.6: 1.25.
218.18kg of HCN (content 99%, purity 216kg, 8kmol), 334.4kg of anhydrous methanol (content 99.5%, purity 332.8kg, 10.4kmol), cyclohexane as an inert solvent, cooling to-5 ℃, introducing 350.4kg of hydrogen chloride gas, reacting at-5 to-10 ℃, maintaining the temperature after completing introduction, completely separating out the imine salt, adding 591.7kg of anhydrous methanol (content 99.5%, purity 588.8kg, 18.4kmol), maintaining the temperature at 30-40 ℃, and reacting for 24 hours to obtain 669.3kg of trimethyl orthoformate finished product, 99.20%, purity 663.9kg and yield 78.3%. The rest is the same as the eleventh example.
Example sixteen reaction materials were fed in a molar ratio of hydrocyanic acid to methanol to hydrochloric acid of 1: 3.75: 1.2.
Feeding 218.18kg of HCN (the content is 99%, the purity is 216kg, 8kmol), 321.6kg of anhydrous methanol (the content is 99.5%, the purity is 320.0kg, 10.0kmol), cooling to-5 ℃, introducing 350.4kg of hydrogen chloride gas, reacting at the temperature of-5 to-10 ℃, maintaining the temperature after introducing is finished, and after the imine salt is completely separated out, adding 643.2kg of anhydrous methanol (the content is 99.5%, the purity is 640.0kg, 20.0kmol), maintaining the temperature at 40-50 ℃, and reacting for 72 hours to obtain 688.5kg of trimethyl orthoformate finished product, the content is 98.77%, the purity is 680.1kg, and the yield is 80.2%. The rest is the same as the eleventh example.
Example seventeen the molar ratio of the reaction mass was hydrocyanic acid to methanol to hydrochloric acid 1: 3.8: 1.1.
218.18kg of HCN (content 99%, pureness 216kg, 8kmol), 334.4kg of anhydrous methanol (content 99.5%, pureness 332.8kg, 10.4kmol) as a first part, cooling to-5 ℃ by using n-heptane as an inert solvent, introducing 321.2kg of hydrogen chloride gas, reacting at-5 ℃, maintaining the temperature after the introduction is finished, completely separating out the imine salt, adding 643.2kg of anhydrous methanol (content 99.5%, pureness 640.0kg, 20.0kmol) as a second part, maintaining the temperature at 50-60 ℃, and reacting for 60 hours to obtain 695.8kg of trimethyl orthoformate finished product, 99.44%, 691.9kg of pureness and 81.6% of yield. The rest is the same as the eleventh example.
Example eighteen the molar ratio of reaction mass is hydrocyanic acid to methanol to hydrochloric acid 1: 4.0: 1.25.
218.18kg of HCN (content 99%, purity 216kg, 8kmol), 334.4kg of anhydrous methanol (content 99.5%, purity 332.8kg, 10.4kmol) as a first part, cooling to-10 ℃ by using n-heptane as an inert solvent, introducing 365.0kg of hydrogen chloride gas, reacting at-10 to-15 ℃, maintaining the temperature after the introduction is finished, completely separating out the imine salt, adding 694.6kg of anhydrous methanol (content 99.5%, purity 691.0kg, 21.6kmol) as a second part, maintaining the temperature at 40-50 ℃, and reacting for 48 hours to obtain 656.5kg of trimethyl orthoformate finished product, 98.68%, purity 647.8kg and yield 76.4%. The rest is the same as the eleventh example.
Example nineteen reaction masses were prepared in a molar ratio of hydrocyanic acid to methanol to hydrochloric acid of 1: 3.8: 1.2.
218.18kg of HCN (content 99%, pureness 216kg, 8kmol), 334.4kg of anhydrous methanol (content 99.5%, pureness 332.8kg, 10.4kmol) as a first part, cooling to 0 ℃ by using n-heptane as an inert solvent, introducing 350.4kg of hydrogen chloride gas, reacting at 0-10 ℃, maintaining the temperature after the introduction is finished, and after imine salt is completely separated out, adding 643.2kg of anhydrous methanol (content 99.5%, pureness 640.0kg, 20kmol) as a second part, keeping the temperature at 30-40 ℃, and reacting for 36 hours to obtain 667.2kg of trimethyl orthoformate finished product, the content 99.00%, the pureness 660.5kg and the yield of 77.9%. The rest is the same as the eleventh example.
Example twenty the molar ratio of reaction mass was hydrocyanic acid to methanol to hydrochloric acid 1: 3.75: 1.3.
218.18kg of HCN (content 99%, purity 216kg, 8kmol), 347.3kg of anhydrous methanol (content 99.5%, purity 345.6kg, 10.8kmol) are added, the temperature is reduced to-5 ℃, 379.6kg of hydrogen chloride gas is introduced, the reaction temperature is-5 to 10 ℃, after introduction is finished, the temperature is maintained, after the imine salt is completely separated out, 617.4kg of anhydrous methanol (content 99.5%, purity 614.4kg, 19.2kmol) is added, the temperature is maintained at 30 to 40 ℃, and the reaction is carried out for 24 hours, so that 678.5kg of trimethyl orthoformate finished products, the content 98.35%, purity 667.3kg and the yield 78.7% are obtained. The rest is the same as the eleventh example.
Claims (3)
1. A process for preparing orthoformate from hydrocyanic acid as the waste gas of acrylonitrile plant features that hydrocyanic acid is used as initial raw material, and then salified with alcohol and hydrohalic acid in inertial solvent, alcoholysis, crystallization separation and rectification, and the molar ratio of hydrocyanic acid to alcohol to hydrohalic acid is 1: 3.5-4.0: 1.1-1.25, the reaction temp is-20-10 deg.C, the reaction temp in alcoholysis step is 30-60 deg.C, and the reaction time is 24-72 hr.
2. A process according to claim 1, wherein trimethyl orthoformate is obtained using methanol.
3. A process according to claim 1 wherein the triethyl orthoformate is obtained using ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001113143A CN1163462C (en) | 2000-08-24 | 2000-08-24 | Process for preparing orthoformate from hydrocyanic acid as waste gas of acrylonitrile plant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001113143A CN1163462C (en) | 2000-08-24 | 2000-08-24 | Process for preparing orthoformate from hydrocyanic acid as waste gas of acrylonitrile plant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1340495A true CN1340495A (en) | 2002-03-20 |
| CN1163462C CN1163462C (en) | 2004-08-25 |
Family
ID=4581235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001113143A Expired - Lifetime CN1163462C (en) | 2000-08-24 | 2000-08-24 | Process for preparing orthoformate from hydrocyanic acid as waste gas of acrylonitrile plant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1163462C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320168C (en) * | 2001-09-21 | 2007-06-06 | 巴斯福股份公司 | Method for producing orthocarboxylic acid trialkyl esters |
| CN102367221A (en) * | 2011-09-01 | 2012-03-07 | 重庆紫光化工股份有限公司 | Preparation method of ortho-formate |
| CN102701925A (en) * | 2012-06-26 | 2012-10-03 | 重庆紫光化工股份有限公司 | Method for purifying ortho-formate |
| CN101717351B (en) * | 2009-12-02 | 2013-01-09 | 淄博万昌科技股份有限公司 | Method for preparing formamidine acetate |
| CN103739463A (en) * | 2014-01-02 | 2014-04-23 | 淄博万昌科技股份有限公司 | Simple and convenient method for producing high-purity ortho-formate |
| CN110872214A (en) * | 2018-08-30 | 2020-03-10 | 重庆紫光化工股份有限公司 | Trimethyl orthoformate and preparation method thereof |
| CN112979433A (en) * | 2021-03-11 | 2021-06-18 | 临沭县华盛化工有限公司 | Control method in triethyl orthoformate synthesis process |
-
2000
- 2000-08-24 CN CNB001113143A patent/CN1163462C/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320168C (en) * | 2001-09-21 | 2007-06-06 | 巴斯福股份公司 | Method for producing orthocarboxylic acid trialkyl esters |
| CN101717351B (en) * | 2009-12-02 | 2013-01-09 | 淄博万昌科技股份有限公司 | Method for preparing formamidine acetate |
| CN102367221A (en) * | 2011-09-01 | 2012-03-07 | 重庆紫光化工股份有限公司 | Preparation method of ortho-formate |
| CN102701925A (en) * | 2012-06-26 | 2012-10-03 | 重庆紫光化工股份有限公司 | Method for purifying ortho-formate |
| CN103739463A (en) * | 2014-01-02 | 2014-04-23 | 淄博万昌科技股份有限公司 | Simple and convenient method for producing high-purity ortho-formate |
| CN103739463B (en) * | 2014-01-02 | 2017-11-17 | 山东未名天源生物科技有限公司 | A kind of short-cut method for producing high purity raw formic acid esters |
| CN110872214A (en) * | 2018-08-30 | 2020-03-10 | 重庆紫光化工股份有限公司 | Trimethyl orthoformate and preparation method thereof |
| CN110872214B (en) * | 2018-08-30 | 2021-08-13 | 重庆紫光化工股份有限公司 | Trimethyl orthoformate and preparation method thereof |
| CN112979433A (en) * | 2021-03-11 | 2021-06-18 | 临沭县华盛化工有限公司 | Control method in triethyl orthoformate synthesis process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1163462C (en) | 2004-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1232502C (en) | Process for producing nateglinide crystal | |
| CN1163462C (en) | Process for preparing orthoformate from hydrocyanic acid as waste gas of acrylonitrile plant | |
| CN113321598A (en) | Preparation method of acetamidine hydrochloride | |
| CN113200882A (en) | Glycine crystallization method without alcohol precipitation | |
| CN112300210A (en) | Production process of spermine | |
| CN108456143A (en) | Asymmetry prepares (S) -3- aminomethyl -5- methylhexanoic acids | |
| CN100336846C (en) | Production method of poly ammonium phosphate | |
| CN1657516A (en) | Process for preparing high-purity orthoformate | |
| CN1903830A (en) | Preparation method of 2-bromo-2-nitro-1,3-propylene glycol | |
| CN109721496B (en) | Synthetic method of 3-nitro-o-xylene | |
| CN112940022B (en) | Preparation method of dimethylamine borane | |
| CN1552685A (en) | Environmental protection cleaning process method for producing high-purity orthoformate | |
| CN1042722C (en) | Non-recovery process for producing potassium sulphate by Mannheim furnace | |
| CN1465688A (en) | Distille's yeast for brewing magma fruit liquor | |
| CN1180066A (en) | Chloroacetic acid producing process | |
| CN1075480C (en) | Method for producing sulfonyl nitrogen-potassium compound fertilizer | |
| CN1196684C (en) | Process for producing N.N'-carbonyl dilactan | |
| CN1291182A (en) | Process for producing highly pure tetrasodium salt of ethylenediaminetetracetic acid | |
| CN115850113B (en) | Synthesis method of L-caprolaconitrile | |
| CN1345299A (en) | Method for production of aiphatic fluoroformates | |
| CN1276341A (en) | Process for preparing silica white using sodium fluorosilicate as raw material | |
| CN1365968A (en) | Process for equipment for continuously preparing diazonium salt of triarylamine | |
| CN1569799A (en) | Process for preparing high-purity 3-chloropropionic acid | |
| CN1566063A (en) | Production process for chloroacetic acid | |
| CN110183355B (en) | Refining method of high-purity o-chloro mandelonitrile |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| ASS | Succession or assignment of patent right |
Owner name: ZIBO WANCHANG SCIENCE & TECHNOLO GY DEVELOPMENT C Free format text: FORMER OWNER: WANCHANG GROUP CO LTD, ZIBO Effective date: 20020209 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20020209 Address after: 255424, 1 East imperial Road, Linzi District, Shandong, Zibo Applicant after: Zibo Wanchang Technology Development Co., Ltd. Address before: 255424 Zibo wan chang Group Co., Ltd., 1 imperial Road East, Linzi District, Shandong, Zibo Applicant before: Wanchang Group Co Ltd, Zibo |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: ZIBO WANCHANG SCIENCE AND TECHNOLOGY CO., LTD. Free format text: FORMER NAME: ZIBO WANCHANG SCIENCE AND TECHNOLOGY DEVELOPMENT CO., LTD. |
|
| CP03 | Change of name, title or address |
Address after: 255068 Chaoyang Road, Zhangdian District, Shandong, Zibo, China Patentee after: Zibo Wanchang Science & Technology Co., Ltd. Address before: 255424, 1 East imperial Road, Linzi District, Shandong, Zibo Patentee before: Zibo Wanchang Technology Development Co., Ltd. |
|
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 255068 Chaoyang Road, Zhangdian District, Shandong, Zibo, China Patentee after: SHANDONG SINOBIOWAY BIOMEDICINE CO., LTD. Address before: 255068 Chaoyang Road, Zhangdian District, Shandong, Zibo, China Patentee before: Zibo Wanchang Science & Technology Co., Ltd. |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170116 Address after: 255000 Chaoyang Road, Zhangdian District, Shandong, Zibo, China Patentee after: Shandong Weiming Tianyuan Biotechnology Co. Ltd. Address before: 255068 Chaoyang Road, Zhangdian District, Shandong, Zibo, China Patentee before: SHANDONG SINOBIOWAY BIOMEDICINE CO., LTD. |
|
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20040825 |