CN102530868B - Ammonia oxidation synthetic gas is except the environment-protective process method of ammonia - Google Patents
Ammonia oxidation synthetic gas is except the environment-protective process method of ammonia Download PDFInfo
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- CN102530868B CN102530868B CN201010607790.1A CN201010607790A CN102530868B CN 102530868 B CN102530868 B CN 102530868B CN 201010607790 A CN201010607790 A CN 201010607790A CN 102530868 B CN102530868 B CN 102530868B
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Abstract
The present invention is to provide the environment-protective process method of a kind of ammonia oxidation synthetic gas except ammonia, it is characterized in that adopting a kind of technology method of combining except ammonia, is made up of phosphoric acid or the elementary meticulous ammonia that removes of ammonia and sulfuric acid or monoammonium sulfate that removes of primary ammonium phosphate; The elementary of ammonia oxidation synthetic gas removes ammonia, adopt phosphoric acid or primary ammonium phosphate as carrier, the free ammonia absorbed in synthetic gas is removed in ammonia tower elementary, phosphoric acid or primary ammonium phosphate are converted into Secondary ammonium phosphate, Secondary ammonium phosphate parses free ammonia in Analytic Tower, be converted into primary ammonium phosphate again, such iterative cycles achieves the elementary recovery removing ammonia and ammonia of synthetic gas; Ammonia oxidation synthetic gas is by elementary meticulous except ammonia tower except entering after ammonia again, the meticulous ammonia that removes adopts sulfuric acid or monoammonium sulfate as absorption agent, meticulous elementary except the residual ammonia in the synthetic gas after ammonia except absorbing in ammonia tower, sulfuric acid or monoammonium sulfate are converted to ammonium sulfate byproduct, realize the meticulous except ammonia of ammonia oxidation synthetic gas.Not only ammonia oxidation synthetic gas is combined except ammonia, achieves the recycling of ammonia oxidation synthetic gas free ammonia, has saved resource but also has achieved the real feature of environmental protection of ammonia-removal process, had extraordinary economic benefit and social benefit.
Description
Technical field
A kind of ammonia oxidation synthetic gas that relates to is except the environment-protective process method of ammonia, refer at the removal technological process for purifying taking ammonia as the reaction gas free ammonia of ammonia oxidation after its synthesis that ammonia source is carried out, fully take into account the recycling of ammonia and the feature of environmental protection of technological process, belong to environment-friendly clean process technological method.
Background technology
Oxidative ammonolysis is the process known, and it is under the existence of ammoxidation catalyst, can the organism pyrolytic conversion of ammonia oxidation be prussiate with ammonia and oxygen.The technological value application of oxidative ammonolysis than if any: by propylene acrylonitrile production, by toluene benzonitrile, by ortho position or paraxylene phthalonitrile or para-Phthalonitrile, by 3-picoline nicotinonitrile and by methane for prussic acid and hydrogen from methyl alcohol cyanic acid etc.; In the technological process of these technology, usually have the free ammonia of a great deal of in the synthesis gas after oxidative ammonolysis, these free ammonias need to be separated or just can to carry out the purification of product or the reaction of lower step operation after removal.In existing industrial production, the removal of the free ammonia in reaction mixture gas adopts sulfuric acid neutralisation to remove mostly, removes respond well.But owing to adopting sulfuric acid neutralization can produce a large amount of ammonium sulfate byproducts except ammonia, ammonium sulfate is cheap and need to consume a large amount of sulfuric acid except ammonia, and ammonia has also been consumed, ineffective; Industry also there are many kind and upright men imagine the ammonia-removal method adopting other, try hard to recovery ammonia to utilize: such as adopt phosphoric acid as absorption agent, free ammonia is absorbed into Secondary ammonium phosphate, Secondary ammonium phosphate and obtains primary ammonium phosphate release ammonia by parsing again by phosphoric acid, thus reaches the recycling of ammonia.Thisly realize the removal of synthetic gas free ammonia and the method for recycling using phosphoric acid or primary ammonium phosphate as carrier, advantageous effects can be obtained to a certain extent, but due to the stability of Secondary ammonium phosphate be limited; Therefore, adopting phosphoric acid or primary ammonium phosphate to absorb its thoroughness removed of synthetic gas free ammonia can't solve very well, also remains the free ammonia of certain content in the synthetic gas after process; The temperature of synthetic gas system especially is after treatment when higher, and in synthetic gas, the content of residual free ammonia can be higher, is difficult to reach processing requirements; If treatment temp control ratio is lower, so can dissolve other material a certain amount of in treatment solution system, bring other unfavorable factor to parsing pre-treatment and resolving; Therefore being greatly limited property in actual production, can not promote very well.
Summary of the invention
For the deficiency of ammonia oxidation synthetic gas ammonia-removal process technology described above, adopt a kind of associating ammonia-removal process method, both can well realize the recycling of ammonia, and the free ammonia process in synthetic gas can have been obtained again very thorough, achieve the sufficient feature of environmental protection of technological process.
The object of this invention is to provide the environment-protective process method of a kind of ammonia oxidation synthetic gas except ammonia, it is characterized in that adopting a kind of technology method of combining except ammonia, be made up of phosphoric acid or the elementary meticulous ammonia that removes of ammonia and sulfuric acid or monoammonium sulfate that removes of primary ammonium phosphate; The elementary of ammonia oxidation synthetic gas removes ammonia, adopt phosphoric acid or primary ammonium phosphate as carrier, the free ammonia absorbed in synthetic gas is removed in ammonia tower elementary, phosphoric acid or primary ammonium phosphate are converted into Secondary ammonium phosphate, Secondary ammonium phosphate parses free ammonia in Analytic Tower, be converted into primary ammonium phosphate again, such iterative cycles achieves the elementary recovery removing ammonia and ammonia of synthetic gas; Ammonia oxidation synthetic gas is by elementary meticulous except ammonia tower except entering after ammonia again, the meticulous ammonia that removes adopts sulfuric acid or monoammonium sulfate as absorption agent, meticulous elementary except the residual ammonia in the synthetic gas after ammonia except absorbing in ammonia tower, sulfuric acid or monoammonium sulfate are converted to ammonium sulfate byproduct, realize the meticulous except ammonia of ammonia oxidation synthetic gas.
A kind of ammonia oxidation synthetic gas provided by the invention is except the environment-protective process method of ammonia, be applicable to all oxidative ammonolysis synthetic gas that relates to except ammonia process, as by propylene acrylonitrile production, by toluene benzonitrile, by ortho position or paraxylene phthalonitrile or para-Phthalonitrile, remove ammonia process by 3-picoline nicotinonitrile and by methane prepared by ammoxidation for oxidative ammonolysis synthetic gas such as prussic acid and methanol ammonoxidation hydrogen manufacturing cyanic acid; Not only the recycling of ammonia oxidation synthetic gas free ammonia can be realized, can economize on resources but also the real feature of environmental protection of ammonia-removal process can be realized, having extraordinary economic benefit and social benefit.
A kind of ammonia oxidation synthetic gas provided by the invention is except the environment-protective process method of ammonia, and its concrete implementation step is as follows:
The first step: the elementary of ammonia oxidation synthetic gas removes ammonia, realizes the recycling of free ammonia.
Ammonia oxidation synthetic gas enters elementary except ammonia tower, and phosphoric acid or ammonium dihydrogen phosphate aqueous solution are converted into ammonium dibasic phosphate aqueous solution elementary except the free ammonia absorbed in synthetic gas in ammonia tower, and ammonia oxidation synthetic gas realizes elementary except ammonia.Reaction equation is as follows:
NH
3+H
3PO
4——→NH
4H
2PO
4
NH
3+NH
4H
2PO
4——→(NH
4)
2HPO
4
The absorption tower device of the free ammonia in ammonium dihydrogen phosphate aqueous solution absorbing ammonia oxidative synthesis gas is generally divided into two sections; In the epimere circulating absorption solution of absorption tower, determining ammonium biphosphate content is relatively high, and in the hypomere circulating absorption solution of absorption tower, the relative concentration of Secondary ammonium phosphate is higher; The absorption liquid flowed out bottom hypomere absorption tower transforms ammonium dibasic phosphate aqueous solution completely for close.After the epimere circulating absorption solution cyclic absorption ammonia of absorption tower, flowing to hypomere absorption tower from the bottom on epimere absorption tower, then continue cyclic absorption ammonia in hypomere absorption tower, finally flowing out close to transforming ammonium dibasic phosphate aqueous solution completely bottom hypomere absorption tower.
Ammonium dibasic phosphate aqueous solution is resolved release ammonia and is converted to primary ammonium phosphate in Analytic Tower, and primary ammonium phosphate returns elementary except the use of ammonia tower iterative cycles again; The ammonia water of release absorbs and obtains the recycling of ammoniacal liquor for ammonia.Reaction equation is as follows:
(NH
4)
2HPO
4——→NH
4H
2PO
4+NH
3↑
Ammonium dibasic phosphate aqueous solution is resolved release ammonia and is obtained ammonia soln in Analytic Tower, ammonia soln is by ammonia separation retrieving arrangement, obtain the raw material ammonia that can be directly used in ammonia oxidation building-up reactions, achieve recycling and the cleaner production of ammonia oxidation synthesis technique of free ammonia.
Ammonia oxidation synthetic gas by elementary except ammonia can to remove in reaction gas 95% or more free ammonia, adopt this technical matters, the ammonia of 95% or more can be recycled.
The elementary residual volume except ammonia after ammonia of ammonia oxidation synthetic gas, determines with except factors such as ammonia temperature, pressure environment and ammonium dibasic phosphate solution stability, not fairly obvious with ammonia oxidation synthetic gas free ammonia relation with contents; Even if there is more free ammonia also well can be reclaimed by the elementary ammonia that removes in synthetic gas.Therefore in the actual production of enforcement ammonia oxidation building-up reactions, the ratio of increase ammonia that can be suitable in reaction raw materials proportioning, the side reaction in ammonia oxidation building-up reactions can be effectively suppressed to occur, improve overall yield and quality product, solve the consumption of ammonia and the contradiction of quality product and product yield well.
Second step: the meticulous of ammonia oxidation synthetic gas removes ammonia, obtains except ammonia ammonia oxidation synthetic gas comparatively thoroughly.
Enter meticulous except ammonia tower by elementary again except the ammonia oxidation synthetic gas after ammonia, adopt sulfuric acid or monoammonium sulfate as absorption agent, meticulous except ammonia tower in absorb the ammonia of the remnants in synthetic gas, sulfuric acid or monoammonium sulfate are converted to ammonium sulfate byproduct.Reaction equation is as follows:
2NH
3+H
2SO
4——→(NH
4)
2SO
4
NH
3+NH
4HSO
4——→(NH
4)
2SO
4
Because ammonium sulfate is highly stable in system, can realize meticulously removing ammonia except free ammonia remaining in the ammonia oxidation synthetic gas after ammonia absorbs more thoroughly by by phosphate system is elementary, obtain the synthetic gas system required for us, for lower step process and synthesis.Because the elementary amount except free ammonia remaining in the synthetic gas system after ammonia only has 5% or following of the front free ammonia amount of process, so the amount of producing ammonium sulfate byproduct only has merely with 5% during sulfuric acid absorption process or following, this just greatly reduces the market pressure of producing ammonium sulfate byproduct and the consumption of sulfuric acid, also greatly reduce the treatment capacity of producing ammonium sulfate byproduct simultaneously, save energy consumption, achieved cleaning technique and produce.
Technical matters provided by the invention, has following feature:
1. the removal of the free ammonia of ammonia oxidation synthetic gas is divided into two steps to carry out by the present invention, and two combination of steps are removed ammonia and realized the recycling of free ammonia and the thorough removal of synthetic gas free ammonia; Save raw material ammonia and raw material sulphuric acid, save material cost.
2. combine except ammonia can make ammonia oxidation synthetic gas become relatively friendly except the envrionment conditions in ammonia operation, material obtains good improvement to equipment corrosion, can work-ing life of extension device while saving facility investment.
3. combine except ammonia is under the prerequisite economized on resources, very effectively can realize environment-protecting clean and produce, well solve the difficult problem of environmental protection in existing ammonia oxidation synthesis and production process, breach the environmental technology barrier of ammonia oxidation synthesis and production process industrialized development.
4. adopt and combine except ammonia can realize the efficient recovery of ammonia, the ratio of increase ammonia that can be suitable in ammonia oxidation building-up reactions proportioning raw materials, effectively can suppress the side reaction in ammonia oxidation building-up reactions, improve overall yield and quality product, well solve the consumption of ammonia and the contradiction of quality product.
Accompanying drawing explanation
Figure of description is the schematic flow sheet that the oxidative ammonolysis synthetic gas that the present invention relates to combines except ammonia.
Embodiment
Carry out illustrating in greater detail the present invention below by embodiment, but scope of the present invention is not by the restriction of embodiment.
Embodiment: iS-One method Sweet natural gas ammonia oxidation synthesis prussic acid, reacting synthesis gas is by combining except ammonia obtains not containing ammonia or the Reactive Synthesis gas containing constant ammonia.
The component of certain synthetic gas before removing ammonia is as following table:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 0.08092 | 6 | N 2 | 0.54328 |
| 2 | NH 3 | 0.01508 | 7 | CO 2 | 0.00503 |
| 3 | H 2O | 0.25513 | 8 | CO | 0.04705 |
| 4 | CH 4 | 0.00462 | 9 | H 2 | 0.04765 |
| 5 | O 2 | 0.00020 | 10 | Other | 0.00104 |
Synthetic gas by elementary except ammonia realize the recycling of free ammonia after obtain elementary except ammonia synthesis gas, the elementary component except ammonia synthesis gas is as following table:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 0.089855 | 6 | N 2 | 0.608716 |
| 2 | NH 3 | 0.000679 | 7 | CO 2 | 0.005631 |
| 3 | H 2O | 0.182415 | 8 | CO | 0.052714 |
| 4 | CH 4 | 0.005181 | 9 | H 2 | 0.053388 |
| 5 | O 2 | 0.000225 | 10 | Other | 0.001196 |
Elementary is 95.497% except ammonia removes ammonia rate.Ammonium dihydrogen phosphate absorbing ammonia is converted into ammonium hydrogen phosphate solution, by resolving the recovery with ammonia; The ammonium dihydrogen phosphate parsed is cycled to used in the absorption of ammonia, reclaims ammonia and is used for ammonia oxidation raw material; Elementaryly achieve the recycling of ammonia except ammonia.
Elementary except ammonia synthesis gas is again by meticulous meticulous except ammonia synthesis gas except obtaining after ammonia by-product sulfate of ammoniac, the meticulous component except ammonia synthesis gas is as following table:
| Sequence number | Component title | Component ratio % | Sequence number | Component title | Component ratio % |
| 1 | HCN | 0.091558 | 6 | N 2 | 0.621532 |
| 2 | NH 3 | 0.000012 | 7 | CO 2 | 0.005853 |
| 3 | H 2O | 0.166567 | 8 | CO | 0.053628 |
| 4 | CH 4 | 0.005225 | 9 | H 2 | 0.054168 |
| 5 | O 2 | 0.000231 | 10 | Other | 0.001226 |
Meticulous except ammonia except ammonia rate be 98.233%; Monoammonium sulfate or sulphuric acid soln absorbing ammonia are converted into ammoniumsulphate soln, and ammoniumsulphate soln is through purifying treatment and condensing crystal obtains ammonium sulfate byproduct.
Ammonia oxidation synthetic gas except ammonia step realizes combining except ammonia by two, is not only achieved the recycling of ammonia but also achieves the removal of ammonia in synthetic gas.
Claims (1)
1. an ammonia oxidation synthetic gas is except the environment-protective process method of ammonia, it is characterized in that adopting a kind of technology method of combining except ammonia, be applicable to all relate to oxidative ammonolysis synthetic gas except ammonia process, comprise by propylene acrylonitrile production, by toluene benzonitrile, by ortho position or paraxylene phthalonitrile or para-Phthalonitrile, by 3-picoline nicotinonitrile and by methane prepared by ammoxidation for prussic acid and methanol ammonoxidation hydrogen manufacturing cyanic acid oxidative ammonolysis synthetic gas except ammonia process, be made up of phosphoric acid or the elementary meticulous ammonia that removes of ammonia and sulfuric acid or monoammonium sulfate that removes of primary ammonium phosphate, the elementary of ammonia oxidation synthetic gas removes ammonia, realize the recycling of free ammonia: adopt phosphoric acid or primary ammonium phosphate as carrier, the free ammonia absorbed in synthetic gas is removed in ammonia tower elementary, phosphoric acid or primary ammonium phosphate are converted into Secondary ammonium phosphate, Secondary ammonium phosphate parses free ammonia in Analytic Tower, be converted into primary ammonium phosphate again, such iterative cycles achieves the elementary recovery removing ammonia and ammonia of synthetic gas, absorption tower device is divided into two sections, in the epimere circulating absorption solution of absorption tower, determining ammonium biphosphate content is relatively high, in the hypomere circulating absorption solution of absorption tower, the relative concentration of Secondary ammonium phosphate is higher, after the epimere circulating absorption solution cyclic absorption ammonia of absorption tower, hypomere absorption tower is flowed into from the bottom on epimere absorption tower, in hypomere absorption tower, continuing cyclic absorption ammonia again, finally flowing out bottom hypomere absorption tower close to transforming ammonium dibasic phosphate aqueous solution completely, the meticulous of ammonia oxidation synthetic gas removes ammonia, obtain except ammonia ammonia oxidation synthetic gas more thoroughly: ammonia oxidation synthetic gas is by elementary meticulous except ammonia tower except entering after ammonia again, the meticulous ammonia that removes adopts sulfuric acid or monoammonium sulfate as absorption agent, meticulous elementary except the residual ammonia in the synthetic gas after ammonia except absorbing in ammonia tower, sulfuric acid or monoammonium sulfate are converted to ammonium sulfate byproduct, realize the meticulous except ammonia of ammonia oxidation synthetic gas.
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| CN106698344A (en) * | 2015-11-16 | 2017-05-24 | 宁夏琪凯节能设备有限公司 | Energy saving technical process for ammonia removal of ammonia oxidation synthesis gas |
| CN110280104A (en) * | 2019-06-24 | 2019-09-27 | 天华化工机械及自动化研究设计院有限公司 | A kind of phosphorus ammonium method processing catalyst ammonia-contaminated gas and ammonia reclaiming process |
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| CN101027252A (en) * | 2004-07-22 | 2007-08-29 | 伊内奥斯美国公司 | Process for recovery and recycle of ammonia from a vapor stream |
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| Title |
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| 丙烷制丙烯腈工艺中未反应氨的回收方法;BP Amoco;《石油化工》;20001231;第29卷;第238页 * |
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