{ "authors": [], "basis": { "capacity": "50 kt/a THF (ASSUMED)", "location": "generic (not chosen)", "operating_hours_per_year": 8000 }, "benchmarks": [], "chemistry": { "inputs": [ { "chemical": "butane-1-4-diol", "grade": null, "note": "feed:BDOF, 1,4-butanediol (boundary feed, D-003), 1.267 kg/kg THF", "role": "feedstock" }, { "chemical": "p-toluenesulfonic-acid", "grade": null, "note": "feed:PTSAF, p-toluenesulfonic acid catalyst make-up", "role": "feedstock" } ], "outputs": [ { "chemical": "tetrahydrofuran", "grade": null, "inventory_key": "product:THFP", "note": "THF to storage", "role": "main-product" }, { "chemical": "wastewater", "grade": null, "note": "Process water with about 80 ppm(wt) THF to treatment (product:WW, 0.249 kg per kg THF)", "role": "waste" } ], "utilities": [ { "chemical": "steam", "grade": null, "note": "MP steam 1000 kPa(a), R-101 and HP column reboiler (feed:MPS); LP steam 450 kPa(a), LP column trim reboiler (feed:LPS)", "role": "utility" }, { "chemical": "electricity", "grade": null, "note": "Pumps P-101 and P-201 (feed:POWER)", "role": "utility" }, { "chemical": "cooling-water", "grade": null, "note": "25/35 C (ASSUMED), product:CW", "role": "utility" } ] }, "description": "1,4-Butanediol (BDO, a boundary feed) is dehydrated at 145 C and 130 kPa(a) in a stirred,\nsteam-heated reactor with 2 wt% p-toluenesulfonic acid in the liquid, within the ranges of a\npublished reactive-distillation patent (US 9284289 B2). A short rectifying column on the\nreactor holds BDO and heavies back; THF and the water of reaction leave overhead as an\n80 wt% THF condensate. Heavies (lumped as the BDO dimer ether) are held at 30 wt% in the\nreactor liquid by a bleed to incineration, which also removes the acid. The condensate and the\nhigh-pressure column's distillate are separated in a low-pressure column (110 kPa(a)) into\nprocess water and a near-azeotropic distillate, which a high-pressure column (800 kPa(a))\nsplits into THF (99.95 wt%) and a recycle near the high-pressure azeotrope. The high-pressure\ncondenser reboils the low-pressure column.\n\nAll values are concept estimates. The selectivity, bleed and column specifications are\nassumed; the stream and duty values come from an independent script whose property method\n(NRTL with the ChemSep THF/water parameters in thermo) is not qualified by ChemE-as-Code for\nthis mixture yet. The same NRTL parameters predict two liquid phases in part of the\nlow-pressure column's stripping range, while its reflux and duties come from a calculation\nthat assumes one homogeneous liquid, so the LP column duties are unverified; see DESIGN.md of the engineering files for every assumption and gated step.\n", "design_basis": { "assumptions": [ "Route: liquid-phase cyclodehydration of BDO with a homogeneous sulfonic acid (p-toluenesulfonic acid, 2 wt% in the reactor liquid) by reactive distillation at 145 C and 130 kPa(a), within the ranges of US 9284289 B2 (80-250 C, preferred 120-180 C; 0.01-20 wt% acid; 2-8 wt% water in the reactor liquid) (D-001, D-004).", "ASSUMED THF selectivity 0.995 kmol per kmol BDO converted, the rest to heavies lumped as the BDO dimer ether (DHBE); heavies held at 30 wt% in the reactor liquid by a bleed: plant BDO conversion 0.9906, THF yield 0.9857 mol/mol BDO fed (D-005). A sourced conversion/selectivity model is not available; no kinetics.", "ASSUMED pressure-swing distillation: LP column 110 kPa(a), HP column 800 kPa(a); distillates 0.03 mol/mol on the feasible side of each NRTL azeotrope (x_THF 0.827 at 110 kPa(a), 0.651 at 800 kPa(a)); reflux 1.3 x minimum, at least 0.3 (D-007).", "ASSUMED heat integration: the HP column condenser reboils the LP column (E-201), LP steam trims (D-009).", "ASSUMED pump efficiency 0.6; reflux of the reactor rectifying column 0.5 (D-004, D-008).", "All flows, temperatures and duties are concept estimates from an unqualified property method (thermo NRTL, ChemSep THF/water parameters, ideal gas, D-006); accuracy not stated." ], "source": "process/design-basis.yaml" }, "engineering": { "description": "", "name": "Tetrahydrofuran (BDO dehydration)", "requires": "cheme-as-code>=0.8", "stage": "concept", "stages": [ { "id": "concept", "title": "Concept and feasibility" }, { "id": "basic", "title": "Basic engineering" }, { "id": "detail", "title": "Detail engineering" } ], "tool": "plantcode" }, "facets": { "feedstock_basis": [ "fossil" ], "product_classes": [ "chemicals" ], "region": "generic", "unit_operations": [ "reaction", "reactive-distillation", "distillation", "heat-exchange" ] }, "families": [ "oxygenates" ], "gap_count": 3, "gates": null, "id": "thf-1", "issues": { "closed_count": 0, "list_url": "https://github.com/ChemE-as-Code/process-library/issues?q=is%3Aissue%20label%3A%22process%3Athf-1%22", "new": { "action": "https://github.com/ChemE-as-Code/process-library/issues/new?template=1-action-item.yml&labels=process%3Athf-1&process=thf-1", "change": "https://github.com/ChemE-as-Code/process-library/issues/new?template=4-design-change.yml&labels=process%3Athf-1&process=thf-1", "hold": "https://github.com/ChemE-as-Code/process-library/issues/new?template=2-engineering-hold.yml&labels=process%3Athf-1&process=thf-1", "process": "https://github.com/ChemE-as-Code/process-library/issues/new?template=6-process-development.yml&labels=process%3Athf-1&process=thf-1", "tq": "https://github.com/ChemE-as-Code/process-library/issues/new?template=3-technical-query.yml&labels=process%3Athf-1&process=thf-1", "tracker": "https://github.com/ChemE-as-Code/process-library/issues/new?template=7-process-tracker.yml&labels=process%3Athf-1&process=thf-1" }, "open": [], "open_by_gate": {}, "open_count": 0, "private": false, "repository": "ChemE-as-Code/process-library" }, "keywords": [ "tetrahydrofuran", "THF", "1,4-butanediol", "BDO", "cyclodehydration", "reactive distillation", "p-toluenesulfonic acid", "pressure-swing distillation", "azeotrope", "solvent" ], "lca": null, "lci_gaps": [ { "dataset": "tetrahydrofuran-from-1-4-butanediol-50-kt-a-cyclodehydration-and-pressure-swing-distillation", "key": "feed:BDOF", "link": "technosphere", "type": "input" }, { "dataset": "tetrahydrofuran-from-1-4-butanediol-50-kt-a-cyclodehydration-and-pressure-swing-distillation", "key": "feed:PTSAF", "link": "technosphere", "type": "input" }, { "dataset": "tetrahydrofuran-from-1-4-butanediol-50-kt-a-cyclodehydration-and-pressure-swing-distillation", "key": "product:BLEED", "link": "technosphere", "type": "output" } ], "maintainers": [ { "name": "Artur Schweidtmann" } ], "maturity": "concept", "preliminary": true, "provenance": { "library_commit": "c3ab3488c602bc797fdc98feffd4578375150dd0", "previews": { "sheets": [ "BFD", "PFD" ], "source_commit": "c3ab3488c602bc797fdc98feffd4578375150dd0", "tool": "cheme 1.6.0 (pyDEXPI 2.1.0)" }, "previews_stale": false, "source_commit": "c3ab3488c602bc797fdc98feffd4578375150dd0" }, "publication": { "license": "CC-BY-4.0", "status": "public" }, "references": [ { "title": "US 9284289 B2 (Mitsubishi Chemical, 2016) Method for producing tetrahydrofuran (reactive distillation of BDO with a homogeneous sulfonic acid: temperature, catalyst, water ranges; condensate composition)", "url": "https://patents.google.com/patent/US9284289" }, { "doi": "10.1021/jo061017o", "title": "Hunter, S.E.; Ehrenberger, C.E.; Savage, P.E. (2006) Kinetics and mechanism of tetrahydrofuran synthesis via 1,4-butanediol dehydration in high-temperature water. J. Org. Chem. 71, 6229-6239" }, { "doi": "10.3390/ma12132092", "title": "Li, K.-T.; Chen, K.-W. (2019) Cyclodehydration of 1,4-butanediol over Zr-Al catalysts: effect of reaction medium. Materials 12, 2092 (CC BY 4.0)" }, { "doi": "10.1002/14356007.a26_221.pub3", "title": "Ullmann's Encyclopedia of Industrial Chemistry: Tetrahydrofuran (route reference lead; not read in this run)" }, { "title": "ChemSep NRTL binary parameters for THF/water as packaged in thermo 0.6.1 (Caleb Bell et al.), used by scripts/thf_balance.py" } ], "repository": { "access": "public", "path": "processes/thf-1", "url": "https://github.com/ChemE-as-Code/process-library" }, "representations": [ { "bytes": 26062, "id": "BFD", "kind": "bfd", "preview": "artifacts/thf-1/BFD.svg", "source": "process/BFD.xml", "status": "preview", "title": "Block flow diagram" }, { "bytes": 95513, "id": "PFD", "kind": "pfd", "preview": "artifacts/thf-1/PFD.svg", "source": "process/PFD.xml", "status": "preview", "title": "Process flow diagram" }, { "id": "process-model", "kind": "process-model", "source": "process/flowsheet.yaml", "status": "viewer", "title": "Flowsheet and stream table" }, { "id": "equipment-list", "kind": "equipment-list", "source": "equipment/equipment-list.yaml", "status": "viewer", "title": "Equipment list" }, { "id": "lca", "kind": "lca", "source": "lca/lca.yaml", "status": "viewer", "title": "Life cycle assessment" } ], "summary": "Acid-catalysed cyclodehydration of purchased 1,4-butanediol to THF by reactive distillation with homogeneous p-toluenesulfonic acid, then pressure-swing distillation of the THF/water azeotrope at 110 and 800 kPa(a) with condenser-reboiler integration. Concept stage, assumed basis, preliminary gate-to-gate LCI (foreground only).", "title": "Tetrahydrofuran from 1,4-butanediol (50 kt/a, cyclodehydration and pressure-swing distillation)", "validation": { "notes": "Concept PFD with closed mass, component and element balances (cheme validate, cheme process streams, cheme assess lca --balance: mass, C, H, O, S closed to 0.01 %) and an independent overall energy closure of 0.01 % (scripts/thf_balance.py). cheme maturity reaches no level: the feeds and the capacity are assumed (no sourced or owner-given feed), the reactor is a conversion model with an assumed selectivity, and the three columns are specified values from an independent NRTL script that core cannot qualify for THF/water (polar activity-coefficient benchmark, liquid-phase reactor energy). The LCI is a gate-to-gate foreground inventory with every background open (8 gaps): no impact result, and no LCA result passed to the catalog (lca.source none). Not reviewed. Main products and feeds are listed under chemistry with their chemicals registry entries (issue #251).", "status": "unreviewed" }, "viewer": { "commit": "c3ab3488c602bc797fdc98feffd4578375150dd0", "dirty": false, "sheets": [ "process/BFD.xml", "process/PFD.xml" ], "skipped": [], "snapshot": "snapshots/thf-1/", "stale": false, "tool": "cheme-as-code 1.6.0", "views": [ "checks", "streams" ] } }