JP2011006295A - Method for producing carbon monoxide and method for producing phosgene using the same - Google Patents
Method for producing carbon monoxide and method for producing phosgene using the same Download PDFInfo
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 93
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000571 coke Substances 0.000 claims abstract description 35
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- 239000011949 solid catalyst Substances 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 23
- 150000002816 nickel compounds Chemical class 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 150000003464 sulfur compounds Chemical class 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 230000006866 deterioration Effects 0.000 abstract description 8
- 239000007787 solid Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000002344 surface layer Substances 0.000 abstract description 4
- 238000005273 aeration Methods 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- -1 etc. Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101000666896 Homo sapiens V-type immunoglobulin domain-containing suppressor of T-cell activation Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 102100038282 V-type immunoglobulin domain-containing suppressor of T-cell activation Human genes 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000498 cooling water Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- DHEIAYDROZXXGS-UHFFFAOYSA-N ethanol;iodine Chemical compound [I].CCO DHEIAYDROZXXGS-UHFFFAOYSA-N 0.000 description 1
- IJJVMEJXYNJXOJ-UHFFFAOYSA-N fluquinconazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1N1C(=O)C2=CC(F)=CC=C2N=C1N1C=NC=N1 IJJVMEJXYNJXOJ-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
Description
本発明は一酸化炭素の製造方法およびそれを用いたホスゲンの製造方法に関する。更に詳しくは、ニッケル化合物含有量の少ない一酸化炭素の製造方法、および得られた一酸化炭素を用いてホスゲンを製造する方法に関する。また、一酸化炭素（ＣＯ）と塩素（Ｃｌ２）とを固体触媒上で反応させてホスゲンを製造する際、ニッケルを含有する固体の化合物が、固体触媒表層や間隙に詰まることによる固体触媒層の圧力損失上昇および固体触媒の劣化を抑制し、コスト的に有利でかつ生産効率の優れたホスゲンの製造方法に関する。 The present invention relates to a method for producing carbon monoxide and a method for producing phosgene using the same. More specifically, the present invention relates to a method for producing carbon monoxide with a low nickel compound content, and a method for producing phosgene using the obtained carbon monoxide. Further, when phosgene is produced by reacting carbon monoxide (CO) and chlorine (Cl 2 ) on a solid catalyst, the solid catalyst layer is formed by solid compounds containing nickel clogging the solid catalyst surface layer or gaps. The present invention relates to a method for producing phosgene that suppresses an increase in pressure loss and deterioration of a solid catalyst, is advantageous in cost, and has excellent production efficiency.
工業的に一酸化炭素を製造する方法として、コークスを酸化する方法が一般に知られている。その一酸化炭素中には様々な不純物が含まれており、幾つかの一酸化炭素製造（精製）方法が提案されている。さらに、その一酸化炭素を用いてホスゲンを製造する方法として、固体触媒に活性炭を用いて塩素と反応させて製造する種々の方法が提案されている。 As a method for industrially producing carbon monoxide, a method for oxidizing coke is generally known. The carbon monoxide contains various impurities, and several carbon monoxide production (purification) methods have been proposed. Furthermore, as a method for producing phosgene using the carbon monoxide, various methods for producing by reacting with chlorine using activated carbon as a solid catalyst have been proposed.
例えば、特許文献１〜４にはホスゲン製造用に一酸化炭素の製造（精製）方法が提案されている。しかしながら、何れの方法においても、一酸化炭素中のニッケル（Ｎｉ）化合物を圧力損失上昇抑制可能な濃度まで除去することができず、この一酸化炭素を用いてホスゲンを製造する場合、ニッケルを含有する固体の化合物が、固体触媒表層や間隙に詰まることによる圧力損失上昇および固体触媒の劣化が促進され、固体触媒の寿命が短くなるため、コスト的に不利で、かつ生産効率が劣るという問題がある。 For example, Patent Documents 1 to 4 propose a method for producing (purifying) carbon monoxide for producing phosgene. However, in any method, the nickel (Ni) compound in carbon monoxide cannot be removed to a concentration capable of suppressing the increase in pressure loss, and when phosgene is produced using this carbon monoxide, nickel is contained. As the solid compound is clogged in the surface layer and the gap of the solid catalyst, the pressure loss increase and the deterioration of the solid catalyst are promoted, and the life of the solid catalyst is shortened, which is disadvantageous in terms of cost and inferior in production efficiency. is there.
本発明の目的は、ホスゲンを製造する際、ニッケルを含有する固体の化合物が固体触媒表層や間隙に詰まることによる圧力損失上昇および固体触媒の劣化を抑制し、固体触媒の更新頻度を少なくして、コスト的に有利で、かつ生産効率の優れたホスゲンの製造方法、およびその原料として用いる一酸化炭素の製造方法を提供することである。 The object of the present invention is to suppress the increase in pressure loss and deterioration of the solid catalyst due to clogging of the solid compound containing nickel in the surface layer and the gap of the solid catalyst when producing phosgene, and reduce the renewal frequency of the solid catalyst. Another object of the present invention is to provide a method for producing phosgene, which is advantageous in terms of cost and excellent in production efficiency, and a method for producing carbon monoxide used as a raw material.
本発明者らは、上記目的を達成せんと鋭意研究した結果、一酸化炭素中に含まれるニッケル化合物が、塩素と反応して固体の化合物を生成し、この固体の化合物が圧力損失の上昇に大きく寄与していたことおよび固体触媒の劣化が促進されることが分かった。さらに、この固体の化合物はコークス中のニッケル含有量に著しく影響されることが分かり、ニッケル含有量の少ないコークスを用いて一酸化炭素を製造することで、ニッケル化合物含有量の少ない一酸化炭素を製造でき、上記目的を達成できることを見出し、本発明に到達した。 As a result of earnest research that the present inventors have achieved the above-mentioned object, the nickel compound contained in carbon monoxide reacts with chlorine to produce a solid compound, which increases the pressure loss. It was found that a large contribution was made and deterioration of the solid catalyst was promoted. Furthermore, it was found that this solid compound was significantly influenced by the nickel content in the coke. Carbon monoxide having a low nickel compound content was produced by producing carbon monoxide using coke having a low nickel content. It has been found that the above object can be achieved and the present invention has been achieved.
すなわち、本発明によれば、
１．コークスに酸素含有ガスを通気することによりコークスを酸化させて一酸化炭素を製造する方法において、ニッケル含有量が３５０重量ｐｐｍ以下のコークスを使用することを特徴とする一酸化炭素の製造方法、
２．一酸化炭素中のニッケル化合物含有量が２０容積ｐｐｍ以下である前項１記載の一酸化炭素の製造方法、
３．前項１記載の方法で得られた一酸化炭素を精製して、ニッケル化合物含有量が０．０５容積ｐｐｍ以下、硫黄化合物含有量が１容積ｐｐｍ以下、露点温度が−２０℃以下、一酸化炭素純度が９５容積％以上である一酸化炭素の製造方法、
４．酸洗浄したコークスを使用することを特徴とする前項１記載の一酸化炭素の製造方法、および
５．前項１記載の方法で得られた一酸化炭素と塩素とを固体触媒を用いて反応させることを特徴とするホスゲンの製造方法、
が提供される。
That is, according to the present invention,
1. In the method for producing carbon monoxide by oxidizing coke by bubbling oxygen-containing gas through coke, a method for producing carbon monoxide, characterized by using coke having a nickel content of 350 ppm by weight or less,
2. The method for producing carbon monoxide according to 1 above, wherein the content of the nickel compound in the carbon monoxide is 20 ppm by volume or less,
3. The carbon monoxide obtained by the method described in the preceding item 1 is purified, the nickel compound content is 0.05 volume ppm or less, the sulfur compound content is 1 volume ppm or less, the dew point temperature is −20 ° C. or less, carbon monoxide. A method for producing carbon monoxide having a purity of 95% by volume or more,
4). 4. A method for producing carbon monoxide according to item 1 above, wherein the acid washed coke is used; A process for producing phosgene, characterized by reacting carbon monoxide obtained by the method of the preceding item 1 and chlorine using a solid catalyst;
Is provided.
本発明によれば、ホスゲンを製造する際、ニッケル化合物による、圧力損失の上昇を抑制し、ホスゲンの生産量の低減を回避することができ、その奏する工業的効果は格別なものである。 According to the present invention, when phosgene is produced, an increase in pressure loss due to the nickel compound can be suppressed, and a reduction in the production amount of phosgene can be avoided, and the industrial effect produced by the phosgene is exceptional.
本発明で使用するコークスは化石燃料由来の原料、例えば石油、石炭等から製造されたものであり、そのニッケル含有量は３５０重量ｐｐｍ以下であり、３００重量ｐｐｍ以下が好ましく、２５０重量ｐｐｍ以下がさらに好ましく、１００重量ｐｐｍ以下が特に好ましい。３５０重量ｐｐｍを超える場合、得られる一酸化炭素中のニッケル化合物濃度が高くなり、その一酸化炭素と塩素とを反応させて、ホスゲンを製造する際、固体触媒層の圧力損失上昇や固体触媒の劣化という問題が生じる。 The coke used in the present invention is produced from a fossil fuel-derived raw material, such as petroleum, coal, etc., and its nickel content is 350 ppm by weight or less, preferably 300 ppm by weight or less, preferably 250 ppm by weight or less. Further preferred is 100 ppm by weight or less. When it exceeds 350 ppm by weight, the concentration of the nickel compound in the obtained carbon monoxide becomes high, and when producing phosgene by reacting the carbon monoxide and chlorine, the increase in pressure loss of the solid catalyst layer and the solid catalyst The problem of deterioration arises.
ニッケル含有量３５０重量ｐｐｍ以下のコークスを得る方法として特に制限は無いが、その１つの方法として酸洗浄する方法が挙げられる。酸洗浄する方法としては例えばコークスを酸に浸漬させる方法やコークスに酸を注ぎかける方法がある。酸洗浄に用いる酸としては、塩酸、硫酸、硝酸、リン酸、フッ酸等の酸を含む水溶液であり、その中で特に塩酸水溶液が好ましい。その水溶液の濃度は０．５ｍｏｌ／Ｌ以上が好ましく、１ｍｏｌ／Ｌ以上がより好ましい。濃度が０．５ｍｏｌ／Ｌより低い場合は、ニッケルの溶出に長時間要することとなる。浸漬時間は３〜１００時間が好ましく、５〜６０時間がより好ましい。浸漬時間が３時間より短い場合はニッケル溶出が不十分な場合があり、１００時間を超える場合は効率が悪くなる。 Although there is no restriction | limiting in particular as a method of obtaining coke with nickel content of 350 weight ppm or less, As one of the methods, the method of acid washing is mentioned. Examples of the acid cleaning method include a method in which coke is immersed in an acid and a method in which acid is poured into the coke. The acid used for the acid cleaning is an aqueous solution containing an acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, and among them, an aqueous hydrochloric acid solution is particularly preferable. The concentration of the aqueous solution is preferably 0.5 mol / L or more, and more preferably 1 mol / L or more. When the concentration is lower than 0.5 mol / L, it takes a long time to elute nickel. The immersion time is preferably 3 to 100 hours, more preferably 5 to 60 hours. When the immersion time is shorter than 3 hours, nickel elution may be insufficient, and when it exceeds 100 hours, the efficiency is deteriorated.
酸洗浄したコークスはｐＨが５〜８になるまで水洗することが好ましい。そのまま使用すると一酸化炭素発生炉等の機器が腐食する可能性があるので水洗をしてｐＨを中性付近にすることが好ましい。水洗浄後のコークスは水分量を０．５重量％以下にする事が好ましい。コークス中に水分量が０．５重量％より多く含まれる場合、反応炉温度の低下による反応効率の悪化や水素発生などの副反応が発生する可能性がある。コークス中のニッケル含有量は、粉砕したコークスに濃硫酸を添加して灰化後、硫酸水素カリウムで融解し、希硝酸に完全に溶解した後、ＩＣＰ発光分析（高周波プラズマ発光分析）法により分析することができる。 The acid washed coke is preferably washed with water until the pH is 5-8. If used as it is, there is a possibility that equipment such as a carbon monoxide generator may corrode, so it is preferable to wash with water to make the pH near neutral. The coke after washing with water preferably has a water content of 0.5% by weight or less. If the amount of water contained in the coke is more than 0.5% by weight, side reactions such as deterioration in reaction efficiency due to a decrease in the reactor temperature and generation of hydrogen may occur. Nickel content in coke is analyzed by ICP emission analysis (high frequency plasma emission analysis) after adding concentrated sulfuric acid to crushed coke, incineration, melting with potassium hydrogen sulfate, and completely dissolving in dilute nitric acid. can do.
コークスと酸素とを反応させて得られる一酸化炭素中にはニッケル化合物が含まれる。一酸化炭素中に含まれるニッケル化合物はニッケルカルボニル（Ｎｉ（ＣＯ）４）等であり、本発明で使用される一酸化炭素中には２０容積ｐｐｍ以下、通常０．０１〜２０容積ｐｐｍ程度存在する。該一酸化炭素中に含まれるニッケルカルボニル等のニッケル化合物は塩素と反応し塩化ニッケル等のニッケルを含有する固体の化合物となり、圧力損失上昇および固体触媒の劣化の原因となる。なお、一酸化炭素中に含まれるニッケル化合物の濃度は、一酸化炭素ガス１００Ｌを、ガス洗浄瓶に入れたヨウ素を溶解させたエタノール、希塩酸および希硝酸（３種類の吸収液を使用）に吸収させて、ＩＣＰ発光分析法より測定される（ＪＩＳ Ｋ−００８３）。 The carbon monoxide obtained by reacting coke with oxygen contains a nickel compound. The nickel compound contained in the carbon monoxide is nickel carbonyl (Ni (CO) 4 ) or the like, and the carbon monoxide used in the present invention has 20 ppm by volume or less, usually about 0.01 to 20 ppm by volume. To do. The nickel compound such as nickel carbonyl contained in the carbon monoxide reacts with chlorine to become a solid compound containing nickel such as nickel chloride, which causes an increase in pressure loss and deterioration of the solid catalyst. The concentration of nickel compound contained in carbon monoxide was absorbed by 100L of carbon monoxide gas in ethanol, dilute hydrochloric acid, and dilute nitric acid (using three types of absorbents) in a gas cleaning bottle. And measured by ICP emission spectrometry (JIS K-0083).
本発明で使用する一酸化炭素は下記の方法で精製することが好ましい。該精製方法として金属添加触媒例えば銅（Ｃｕ）、クロム（Ｃｒ）、バナジウム（Ｖ）、モリブデン（Ｍｏ）等の金属酸化物および／または金属塩を添着した活性炭または活性アルミナ等に接触せしめ、次いで、アルカリ水溶液、例えば水酸化ナトリウム水溶液、水酸化カリウム水溶液、炭酸ナトリウム水溶液、炭酸水素ナトリウム水溶液、炭酸カリウム水溶液、炭酸水素カリウム水溶液と接触させた後、冷却させ、次に活性炭または活性アルミナ等充填槽を通気させて、ニッケル化合物含有量を０．０５容積ｐｐｍ以下、硫黄化合物含有量を１容積ｐｐｍ以下、露点温度を−２０℃以下、一酸化炭素純度を９５容積％以上にすることが好ましい。 The carbon monoxide used in the present invention is preferably purified by the following method. As the purification method, contact is made with a metal addition catalyst such as activated carbon or activated alumina impregnated with metal oxide and / or metal salt such as copper (Cu), chromium (Cr), vanadium (V), molybdenum (Mo), etc. An alkaline aqueous solution such as a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a sodium carbonate aqueous solution, a sodium hydrogen carbonate aqueous solution, a potassium carbonate aqueous solution or a potassium hydrogen carbonate aqueous solution. It is preferable that the nickel compound content is 0.05 volume ppm or less, the sulfur compound content is 1 volume ppm or less, the dew point temperature is −20 ° C. or less, and the carbon monoxide purity is 95 volume% or more.
本発明において、得られた一酸化炭素と塩素とを固体触媒を用いて反応させ、高純度のホスゲンを長期間安定的に製造することができる。ホスゲン製造に用いる固体触媒として活性炭やゼオライトがあり、活性炭が好ましく使用される。活性炭触媒は市販されているものでよく、その比表面積が２００〜１５００ｍ２／ｇで、平均粒径が０．５〜１０ｍｍ、平均長さ１〜１０ｍｍの円柱状のものが好ましく使用される。特に触媒の平均粒径が０．５ｍｍ〜５ｍｍと小さい場合は、ニッケルを含有する固体の化合物が触媒層間隙に詰まり易く、圧力損失の上昇が大きくなり易い。活性炭の具体例としては、例えば日本エンバイロケミカルズ社製白鷺Ｃ２ｘ６／８等が挙げられる。 In the present invention, the obtained carbon monoxide and chlorine can be reacted using a solid catalyst to stably produce high-purity phosgene for a long period of time. As solid catalysts used for phosgene production, there are activated carbon and zeolite, and activated carbon is preferably used. The activated carbon catalyst may be commercially available, and a cylindrical one having a specific surface area of 200 to 1500 m 2 / g, an average particle diameter of 0.5 to 10 mm, and an average length of 1 to 10 mm is preferably used. In particular, when the average particle diameter of the catalyst is as small as 0.5 mm to 5 mm, a solid compound containing nickel tends to clog the catalyst layer gap, and the increase in pressure loss tends to increase. Specific examples of the activated carbon include, for example, Shirahige C 2x 6/8 manufactured by Nippon Enviro Chemicals.
以下に本発明の実施例を示して更に説明するが、本発明はその要旨を超えない限りこれらの実施例に限定されるものではない。なお、一酸化炭素（ＣＯ）の露点、ＣＯ中の硫黄含有量およびニッケル化合物含有量は、下記の方法により測定した。 Examples of the present invention will be further described below, but the present invention is not limited to these examples unless it exceeds the gist. The dew point of carbon monoxide (CO), the sulfur content in CO, and the nickel compound content were measured by the following methods.
（１）コークス中ニッケル含有量：試料を９．８ＭＰａの圧力で圧縮粉砕した。粉砕試料に濃硫酸を添加して灰化後、硫酸水素カリウムで融解した。希硝酸に完全に溶解した後、ＩＣＰ発光分析（高周波プラズマ発光分析）法の検液とし、金属（Ｎｉ）成分の分析を行った。なお、ＩＣＰ発光分析装置はバリアン（株）製 ＶＩＳＴＡ ＭＰ−Ｘを使用した。
（２）ＣＯ中のニッケル化合物含有量；ニッケルカルボニル分析は以下の方法で実施した。まず、ＣＯガス１００Ｌを、ガス洗浄瓶に入れたヨウ素−エタノールに通した後、乾固させた。これを純水に溶解させてＪＩＳ Ｋ−００８３に記載の方法に従って測定した。その他のＣＯ中のニッケル化合物はＪＩＳ Ｋ−００８３に記載の方法で試料採取および分析を行った。
（３）ＣＯ中の硫黄化合物含有量；ガスクロマトグラフ装置（日立製作所製）にＣＯを注入し、硫黄原子含有量として測定した。
（４）ＣＯの露点測定；露点計（桜測器（株）製ＷＴＹ１８０）を用いて測定した。
（５）ＣＯの純度；赤外線式ガス分析計（島津製作所製 ＲＥＡ−２Ｆ）を用いて測定した。
(1) Nickel content in coke: The sample was compressed and pulverized at a pressure of 9.8 MPa. Concentrated sulfuric acid was added to the pulverized sample and incinerated, and then melted with potassium hydrogen sulfate. After completely dissolving in dilute nitric acid, the metal (Ni) component was analyzed as a test solution for ICP emission analysis (high frequency plasma emission analysis). The ICP emission analyzer used was VISTA MP-X manufactured by Varian.
(2) Nickel compound content in CO; nickel carbonyl analysis was carried out by the following method. First, 100 L of CO gas was passed through iodine-ethanol in a gas washing bottle and then dried. This was dissolved in pure water and measured according to the method described in JIS K-0083. Other nickel compounds in CO were sampled and analyzed by the method described in JIS K-0083.
(3) Sulfur compound content in CO; CO was injected into a gas chromatograph apparatus (manufactured by Hitachi, Ltd.) and measured as the sulfur atom content.
(4) CO dew point measurement: Measured using a dew point meter (WTY180 manufactured by Sakura Sokki Co., Ltd.).
(5) Purity of CO: Measured using an infrared gas analyzer (REA-2F manufactured by Shimadzu Corporation).
［実施例１］
コークスはニッケル含有量５００重量ｐｐｍ、平均径５０ｍｍである市販のコークスを破砕して平均径を２５ｍｍ未満として、そのコークスを１ｍｏｌ／Ｌの塩酸水溶液に２４時間浸漬させ、その後水洗したものを使用した。水洗後の水のｐＨは６であった。このコークスをロータリーキルンで１２０℃、２４時間乾燥させた。このコークスの水分含有量は０．３重量％で、ニッケル含有量は１００重量ｐｐｍであった。
[Example 1]
Coke was used by crushing commercially available coke having a nickel content of 500 ppm by weight and an average diameter of 50 mm to make the average diameter less than 25 mm, soaking the coke in a 1 mol / L hydrochloric acid aqueous solution for 24 hours, and then washing with water. . The pH of the water after washing was 6. The coke was dried in a rotary kiln at 120 ° C. for 24 hours. The coke had a water content of 0.3% by weight and a nickel content of 100 ppm by weight.
該コークスを充填した一酸化炭素発生炉内に酸素、二酸化炭素混合ガスを吹き込んで一酸化炭素を製造した。得られたＣＯ（ニッケル化合物含有量１０容積ｐｐｍ）を、クロム（Ｃｒ）等の金属酸化物を添着した活性アルミナに接触せしめ、苛性ソーダ水溶液と向流接触させた後、熱交換器を用いて５℃に冷却させ、次に活性アルミナ充填槽を通気させた。得られたＣＯの純度は９８．５容積％、ＣＯの露点は−４５℃以下、ＣＯ中のニッケル化合物濃度は０．０１容積ｐｐｍ、ＣＯ中の硫黄化合物濃度は０．２容積ｐｐｍ以下であった。 Carbon monoxide was produced by blowing a mixed gas of oxygen and carbon dioxide into a carbon monoxide generator filled with the coke. The obtained CO (nickel compound content: 10 ppm by volume) is brought into contact with activated alumina impregnated with a metal oxide such as chromium (Cr), and is brought into countercurrent contact with an aqueous caustic soda solution. It was allowed to cool to 0 ° C. and then the activated alumina filling vessel was aerated. The purity of the obtained CO was 98.5% by volume, the dew point of CO was −45 ° C. or less, the concentration of nickel compound in CO was 0.01 ppm by volume, and the concentration of sulfur compound in CO was 0.2 ppm by volume or less. It was.
このＣＯを用いてホスゲンを製造するに当たり、ホスゲン反応槽として反応熱を除去する機能を有した多管式反応槽のシェル側に３５℃の冷却水を通水し、チューブ側に活性炭（比表面積１３００ｍ２／ｇ、平均粒径２．７±０．３ｍｍ、平均長さ５．５±０．５ｍｍの日本エンバイロケミカルズ社製白鷺Ｃ２Ｘ６／８）を充填した。この上記の方法により得られたＣＯ１モルに対しＣｌ２０．９７モルの混合ガスを混合器に通した後ホスゲン反応槽に通気して、ホスゲンを１００ｔ生産した。その結果、混合器の入口からホスゲン反応槽出口までのガスの圧力損失は、ホスゲン生産開始時と比べて０．０５ｋＰａ上昇した。 In producing phosgene using this CO, cooling water of 35 ° C. is passed through the shell side of a multi-tubular reaction tank having a function of removing reaction heat as a phosgene reaction tank, and activated carbon (specific surface area) is supplied to the tube side. 1300 m 2 / g, an average particle size of 2.7 ± 0.3 mm, and an average length of 5.5 ± 0.5 mm were manufactured by Nippon Enviro Chemicals Co., Ltd. Hakuho C 2X 6/8). A mixed gas of 0.97 mol of Cl 2 with respect to 1 mol of CO obtained by the above method was passed through a mixer and then vented to a phosgene reaction tank to produce 100 t of phosgene. As a result, the pressure loss of gas from the inlet of the mixer to the outlet of the phosgene reaction vessel increased by 0.05 kPa compared to when phosgene production was started.
［実施例２］
実施例１で用いたＮｉ含有量１００重量ｐｐｍのコークスと市販のＮｉ含有量５００重量ｐｐｍのものを２：１の割合で混合したコークスを使用した以外は実施例１と同じ方法でＣＯを製造した。得られたＣＯの純度は９８．５容積％、ＣＯの露点は−４５℃以下、ＣＯ中のニッケル化合物濃度は０．０２容積ｐｐｍ、ＣＯ中の硫黄化合物濃度は０．２容積ｐｐｍ以下であった。そのＣＯを用いてホスゲンを１００ｔ生産し、その結果、混合器の入口からホスゲン反応槽出口までのガスの圧力損失は、ホスゲン生産開始時と比べて０．０５ｋＰａ上昇した。
[Example 2]
CO was produced in the same manner as in Example 1 except that coke having a Ni content of 100 ppm by weight used in Example 1 and a commercially available Ni content of 500 ppm by weight were mixed at a ratio of 2: 1. did. The purity of the obtained CO was 98.5% by volume, the dew point of CO was −45 ° C. or less, the concentration of nickel compound in CO was 0.02 ppm by volume, and the concentration of sulfur compound in CO was 0.2 ppm by volume or less. It was. The CO was used to produce 100 tons of phosgene. As a result, the pressure loss of gas from the mixer inlet to the phosgene reactor outlet increased by 0.05 kPa compared to the start of phosgene production.
［実施例３］
実施例１で用いたＮｉ含有量１００重量ｐｐｍのコークスと市販のＮｉ含有量５００重量ｐｐｍのものを１：１の割合で混合したコークスを使用した以外は実施例１と同じ方法でＣＯを製造した。得られたＣＯの純度は９８．５容積％、ＣＯの露点は−４５℃以下、ＣＯ中のニッケル化合物濃度は０．０４容積ｐｐｍ、ＣＯ中の硫黄化合物濃度は０．２容積ｐｐｍ以下であった。そのＣＯを用いてホスゲンを１００ｔ生産し、その結果、混合器の入口からホスゲン反応槽出口までのガスの圧力損失は、ホスゲン生産開始時と比べて０．３ｋＰａ上昇した。
[Example 3]
CO was produced in the same manner as in Example 1 except that coke having a Ni content of 100 ppm by weight used in Example 1 and a commercially available Ni content of 500 ppm by weight were mixed at a ratio of 1: 1. did. The purity of the obtained CO was 98.5% by volume, the dew point of CO was −45 ° C. or less, the concentration of nickel compound in CO was 0.04 ppm by volume, and the concentration of sulfur compound in CO was 0.2 ppm by volume or less. It was. The CO was used to produce 100 tons of phosgene. As a result, the pressure loss of gas from the mixer inlet to the phosgene reactor outlet increased by 0.3 kPa compared to the time when phosgene production was started.
［比較例１］
実施例１で用いたＮｉ含有量１００重量ｐｐｍのコークスと市販のＮｉ含有量５００重量ｐｐｍのものを１：２の割合で混合したコークスを使用した以外は実施例１と同じ方法でＣＯを製造した。得られたＣＯの純度は９８．５容積％、ＣＯの露点は−４５℃以下、ＣＯ中のニッケル化合物濃度は０．１０容積ｐｐｍ、ＣＯ中の硫黄化合物濃度は０．２容積ｐｐｍ以下であった。そのＣＯを用いて、ホスゲンを１００ｔ生産した。その結果、混合器の入口からホスゲン反応槽出口までのガスの圧力損失は、ホスゲン生産開始時と比べて１．０ｋＰａ上昇した。
[Comparative Example 1]
CO was produced in the same manner as in Example 1 except that coke having a Ni content of 100 ppm by weight used in Example 1 and a commercially available Ni content of 500 ppm by weight in a ratio of 1: 2 was used. did. The purity of the obtained CO was 98.5% by volume, the dew point of CO was −45 ° C. or less, the concentration of nickel compound in CO was 0.10 ppm by volume, and the concentration of sulfur compound in CO was 0.2 ppm by volume or less. It was. 100t of phosgene was produced using the CO. As a result, the pressure loss of the gas from the mixer inlet to the phosgene reactor outlet increased by 1.0 kPa compared to when phosgene production was started.
［比較例２］
市販コークスでＮｉ含有量５００重量ｐｐｍのものを使用した以外は実施例１と同じ方法でＣＯを製造した。得られたＣＯの純度は９８．５容積％、ＣＯの露点は−４５℃以下、ＣＯ中のニッケル化合物濃度は０．１２容積ｐｐｍ、ＣＯ中の硫黄化合物濃度は０．２容積ｐｐｍ以下であった。そのＣＯを用いてホスゲンを１００ｔ生産した。その結果、混合器の入口からホスゲン反応槽出口までのガスの圧力損失は、ホスゲン生産開始時と比べて１．５ｋＰａ上昇した。
[Comparative Example 2]
CO was produced in the same manner as in Example 1 except that commercially available coke having a Ni content of 500 ppm by weight was used. The purity of the obtained CO was 98.5% by volume, the dew point of CO was −45 ° C. or less, the concentration of nickel compound in CO was 0.12 ppm by volume, and the concentration of sulfur compound in CO was 0.2 ppm by volume or less. It was. 100t of phosgene was produced using the CO. As a result, the pressure loss of the gas from the mixer inlet to the phosgene reactor outlet increased by 1.5 kPa compared to when phosgene production was started.
本発明で製造された一酸化炭素およびホスゲンは、ポリカーボネート樹脂の製造原料等として有用である。 Carbon monoxide and phosgene produced in the present invention are useful as raw materials for producing polycarbonate resins.
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| Title |
|---|
| JPN6013020632; ＷＡＬＳＨ，Ｄ．Ｅ． ｅｔ ａｌ: 'Ａ ｌａｂｏｒａｔｏｒｙ ｓｔｕｄｙ ｏｆ ｐｅｔｒｏｌｅｕｍ ｃｏｋｅ ｃｏｍｂｕｓｔｉｏｎ． Ｋｉｎｅｔｉｃｓ ａｎｄ ｃａｔａｌｙｔｉｃ ｅｆｆｅｃｔｓ' Ｉｎｄｕｓｔｒｉａｌ ＆ Ｅｎｇｉｎｅｅｒｉｎｇ Ｃｈｅｍｉｓｔｒｙ Ｒｅｓｅａｒｃｈ Ｖｏｌ．２７， Ｎｏ．７, 1988, ｐ．１１１５-１１２０ * |
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| CN101927999A (en) | 2010-12-29 |
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